CN115838607A - Hydrogenation stabilizing method for joint recovery of different distillation range coal liquefied oil zone reaction products - Google Patents
Hydrogenation stabilizing method for joint recovery of different distillation range coal liquefied oil zone reaction products Download PDFInfo
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A hydrogenation stabilization method for joint recovery of coal liquefaction oil products with different distillation ranges comprises the steps of respectively introducing heavy fraction coal liquefaction oil rich in high-order aromatic hydrocarbon and light fraction coal liquefaction oil poor in high-order aromatic hydrocarbon into a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, wherein DV1 is a limited expansion bed reaction mode, so that respective optimal hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out, the hydrogen supply index of a hydrogen supply solvent is improved, and the coal liquefaction efficiency is improved; coking materials and metal deposits of high-order aromatic hydrocarbons are concentrated in the catalyst in the DV1, so that the aging and replacement speed of the catalyst in the DV2 can be remarkably reduced; the catalyst replacement speed in DV1 can be increased, and high-quality equilibrium catalyst can be maintained; jointly recovering a hydrogen-rich gas in the DV1 reaction product and the DV2 reaction product and/or jointly recovering a liquid which is rich in hydrogen-supplying hydrocarbon in the DV1 reaction product and the DV2 reaction product; part of the reaction product liquid can be used as the circulating oil of the sub-reaction zone.
Description
Technical Field
The invention relates to a hydrogenation stabilizing method for joint recovery of different distillation range coal liquefied oil zone reaction products, which is characterized in that heavy fraction coal liquefied oil rich in high-order aromatic hydrocarbon and light fraction coal liquefied oil poor in high-order aromatic hydrocarbon are respectively introduced into a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, DV1 is a limited expansion bed reaction mode, respective optimal hydrogenation stabilizing reactions of different aromatic hydrocarbon saturation depths are carried out, the hydrogen supply index of a hydrogen supply solvent is improved, and the coal liquefaction efficiency is improved; coking materials and metal deposits of high-order aromatic hydrocarbons are concentrated in the catalyst in the DV1, so that the aging and replacement speed of the catalyst in the DV2 can be remarkably reduced; the catalyst replacement speed in DV1 can be increased, and high-quality equilibrium catalyst can be maintained; jointly recovering a hydrogen-rich gas in the DV1 reaction product and the DV2 reaction product and/or jointly recovering a liquid which is rich in hydrogen-supplying hydrocarbon in the DV1 reaction product and the DV2 reaction product; part of the reaction product liquid can be used as the circulating oil of the sub-reaction zone.
Background
The constrained expanded bed reactor of the present invention refers to a reactor in which a stream passes through a particulate catalyst bed in an upflow manner to keep the particulate catalyst bed in an expanded state and catalyst particles in a reaction zone of the expanded bed are not discharged from the reaction zone in a normal operation state, i.e., in a "constrained" state, and thus, the constrained expanded bed of the present invention does not include an operation mode for carrying solid catalyst particles out of the reactor in a normal operation state. The operation mode of the limited expansion bed reactor can be an operation mode of an ebullated bed or a lower bed expansion ratio.
The low-order aromatic hydrocarbon refers to aromatic hydrocarbon with a monocyclic, bicyclic or tricyclic structure.
The high-order aromatic hydrocarbon refers to aromatic hydrocarbon with four rings and more ring structures.
The hydrogen donor refers to a hydrocarbon component having a hydrogen donor function in the direct coal hydrogenation liquefaction reaction process, and the hydrogen donor includes partially saturated bicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons, the cycloalkyl aromatic hydrocarbons can also be called aryl cycloalkanes, hydrogen on the cycloalkane carbon of the aryl cycloalkane has a hydrogen donor capacity, and the aryl provides aromaticity.
The aromatic carbon number fa herein is a ratio of the number of carbon atoms belonging to an aromatic structure to the total number of carbon atoms in the molecular structure.
The aromatic carbon fa calculation formula: f. of a ＝(C/H－H α /2－H β /2－H γ /3)/(C/H)
Wherein C/H is the atomic ratio of carbon to hydrogen; h α Is the fraction of the number of hydrogen atoms connected with the carbon atom at the alpha position of the aromatic ring side chain in the total number of the hydrogen atoms; h β Is the fraction of the number of hydrogen atoms connected to the beta-carbon atom or to the more remote methylene or methine carbon of the side chain of the aromatic ring relative to the total number of hydrogen atoms; h γ The number of hydrogen atoms which are gamma-position of alkyl or combined with methyl carbon at gamma-position or more than gamma-position of aromatic ring side chain is the fraction of the total number of hydrogen atoms.
The hydrogen supply index (proton Donor quality index) PDQI is reported as milligrams of active hydrogen at the beta position of the cycloalkyl group on the cycloalkyl aromatic hydrocarbon per gram of solvent.
Calculating formula of hydrogen supply index PDQI: PDQI = w (H). 10. H nβ /H T
In the formula, w (H) is the content of H element, wt%; h nβ Is composed of 1 An integral value of chemical shift in an interval of 1.5-2.0 in an H-NMR spectrum; h T Is composed of 1 Integral value of all H in H-NMR spectrum; the C atoms at the alpha position and the beta position have 2H atoms, but each C atom can only provide 1H atom, and the numbers of the C atoms at the alpha position and the beta position of the cycloparaffin connected with the aromatic ring on the hydrogenated aromatic hydrocarbon are consistent, so that the integral value of all the H atoms at the beta position in the formula represents all the available hydrogen on the cycloparaffin.
The coal liquefaction oil refers to the distillation oil obtained by removing the distillation residue from the oil fraction generated by the direct liquefaction of coal through hydrogenation, namely the distillation oil after removing the coal liquefaction residue, and can be one path of distillation oil or the mixed oil of a plurality of paths of distillation oil or the mixed oil of all the distillation oil.
The coal liquefaction oil with different distillation ranges is distilled oil with 2 or more different distillation ranges, which is obtained by removing distillation residues from the oil distillation part generated by direct coal hydrogenation liquefaction, namely coal liquefaction residues.
The light fraction coal liquefied oil belongs to high-order aromatic hydrocarbon-lean coal liquefied oil rich in low-order aromatic hydrocarbons with 2-ring and 3-ring structures, mainly comprises hydrocarbon components with conventional boiling points of 200-330 ℃, and because organic metal generally exists in high-boiling-point hydrocarbons, the organic metal content of the light fraction coal liquefied oil is very low.
The heavy fraction coal liquefied oil belongs to low-order aromatic hydrocarbon-poor coal liquefied oil rich in high-order aromatic hydrocarbon, mainly comprises hydrocarbon components with the conventional boiling point of 330-530 ℃, and the organic metal content of the heavy fraction coal liquefied oil is much higher than that of the light fraction coal liquefied oil.
The distillation range overlapping degree between coal liquefaction oil distillate oils with different distillation ranges at adjacent positions of the fractionating tower is higher because the oil distillation part generated by coal hydrogenation direct liquefaction does not need the separation precision of narrow fraction distillate oil, namely belongs to crude distillation.
Because the reflux liquid in the distillation tower has a washing effect on ascending hydrocarbon steam, ascending gas carrying coal dust and flashed from the coal liquefaction product oil containing the heaviest product in a flash evaporation section in the distillation tower generally passes through the washing section to remove the coal dust and then continuously ascends to enter a rectification section to fractionate 1 or more narrow fraction distillate oils which do not contain or basically do not contain the coal dust in a normal operation state, namely, the narrow fraction distillate oil closest to the flash evaporation section of the coal liquefaction product oil containing the heaviest coal hydrogenation direct liquefaction reaction product has the largest probability of containing the coal dust and the largest carrying amount of the coal dust when the production fluctuates.
As mentioned above, the coal liquefied oil of the present invention comprises distillate oil with different distillation ranges discharged from different positions of each fractionating tower above the feed inlet containing the heaviest distillation range feed, and is formed by discharging narrow fraction condensed oil with different distillation ranges separated in the hydrocarbon oil vapor condensation process in each fractionating tower from each fractionating tower.
Table 1 lists properties of raw oil and raw oil narrow-cut segments of a coal liquefaction oil hydrogenation stabilizer produced by a Shenhua coal direct liquefaction device. Table 2 shows the crude oils and their metal contents of the fractions >350 ℃ in Table 1.
The data in tables 1 and 2 are derived from document a01: (1) publication name: direct coal liquefaction Process and engineering, page 261; (2) encoding the search graph: ISBN encoding: 9-78703-04308-23; (3) and (3) compiling: wu Xiu Chao, shu Gong Ping, li Ke Jian and Xishun Ming; (4) the publishing company: scientific press.
As can be seen from Table 1, the feedstock oil has the characteristics of high density, high oxygen content, nitrogen content, aromatic hydrocarbon content and low sulfur content; the yield of the fraction at the temperature of more than 350 ℃ in the raw oil is 31.82 percent, the yield of the fraction at the temperature of 200-350 ℃ is 59.32 percent, and the weight flow rate of the fraction at the temperature of 200-350 ℃ is 1.86 times of the weight flow rate of the fraction at the temperature of more than 350 ℃.
As can be seen from Table 2, the feed oil contains heavy metals and is mainly concentrated in the >350 ℃ fraction.
As is clear from Table 1, the aromatic carbon rate of the fraction at >350 ℃ is 80.76mol%, the aromatic carbon rate of the fraction at 200 to 350 ℃ is 46.26mol%, and the aromatic carbon rate of the ideal hydrogen-donating solvent is usually 0.3 to 0.4 and preferably close to 0.4, and therefore, the optimum aromatic saturation depth of the fraction at >350 ℃ and the optimum aromatic saturation depth of the fraction at 200 to 350 ℃ are inevitably greatly different from each other; due to the difference of molecular structures, the optimal reaction conditions of partial hydrogenation saturation reaction processes of the aromatic hydrocarbon of tricyclic aromatic anthracene (normal boiling point 340 ℃) and tetracyclic aromatic butadience (normal boiling point 450 ℃) are greatly different.
The narrow fractions of the coal liquefied oil with different distillation ranges have different distillation ranges and different aromatic hydrocarbon ring numbers, the content difference of impurity components such as un-liquefied coal dust and organic metal is large, and the coal liquefied oil distillate with the highest boiling range contains not only the most high-order aromatic hydrocarbon and colloid but also a small amount of un-liquefied coal dust and organic metal; when short-term operation fluctuation occurs in the atmospheric and vacuum fractionation part of the coal hydrogenation liquefaction device, the content of coal dust in the coal liquefaction oil can be increased violently; for the reasons, the coal liquefaction oil hydrogenation stabilizing reactor adopts an upflow type limited expansion bed such as a boiling bed reactor which allows coal dust carried in raw materials to freely pass through so as to ensure the continuous operation of the reactor.
TABLE 1 Properties of the stock oils
TABLE 2 crude oil and its metal content in fractions greater than 350 deg.C (unit: mug/g)
| Metal | Ca | Na | V | Fe | Ni |
| Raw oil | 2.45 | 0.24 | 0.02 | 0.29 | 0.01 |
| Fraction at >350 DEG C | 2.49 | 0.82 | 0.16 | 4.60 | 0.04 |
In a coal liquefied oil hydrogenation stable expansion bed reactor in a single reaction zone, the coal liquefied oil used as a raw material in the hydrogenation stable reaction process is usually a mixed oil of multiple narrow-fraction coal liquefied oils with different distillation ranges, which all participate in the hydrogenation stable reaction process, and the mixed oil comprises a gasoline fraction with a conventional boiling point of 50-200 ℃, a diesel oil fraction with a temperature of 200-350 ℃ and a wax oil fraction with a temperature of 350-530 ℃, wherein a high boiling range fraction also comprises un-liquefied coal powder and relatively more organic metals.
The hydrogenation stabilization reaction process of the liquefied oil refers to a hydrogenation modification reaction process of coal liquefied oil, and the main purpose of the hydrogenation stabilization reaction process is to make a bicyclic aromatic hydrocarbon component and/or a polycyclic aromatic hydrocarbon component in the coal liquefied oil undergo a partial aromatic hydrocarbon hydrogenation saturation reaction to convert cycloalkyl aromatic hydrocarbon, namely hydrogen-supplying hydrocarbon; in the direct coal hydrogenation liquefaction reaction process, the hydrogen-donating hydrocarbon not only has aromaticity so as to have good hot melting capacity on coal, but also has hydrogen-donating capacity for providing active hydrogen for coal hot melting and pyrolysis product free radicals to stabilize the coal; and separating the hydrogenation stabilization reaction product of the liquefied oil to obtain a hydrogen supply solvent containing hydrogen supply hydrocarbon, wherein the higher the concentration of the hydrogen supply hydrocarbon in the hydrogen supply solvent is, the higher the liquefaction oil yield of the coal organic matter in the coal liquefaction reaction process is, and the higher the hydrogen content of the coal liquefied oil is.
For a liquefied oil hydro-stabilization process, see document a01: (1) publication name: direct coal liquefaction process and engineering, pages 240-364; (2) encoding a search graph: ISBN encoding: 9-78703-04308-23; (3) and (3) compiling: wu Xiu Chao, shu Gong Ping, li Ke Jian and Xishun Ming; (4) the publishing company: scientific press; the raw oil, hydrogenation stabilization reaction target, hydrogenation stabilization reactor structure, operation condition and working mode of a liquefied oil hydrogenation stabilization device matched with a 100 ten thousand ton/year coal hydrogenation direct liquefaction device of China Shenhua Ordos coal oil production company are described in detail, all distillate oil used as raw oil of the hydrogenation stabilization device from an atmospheric fractionating tower C-301 system and a reduced pressure fractionating tower C-302 system of coal hydrogenation direct liquefaction generated oil are mixed into a path of mixed oil and enter a single reaction zone boiling bed hydrogenation reactor adopted by the hydrogenation stabilization device for treatment, a top liquid collecting cup and a circulating oil guide pipe connected with the lower part of the top liquid collecting cup are arranged in the boiling bed hydrogenation stabilization reactor, a circulating oil pump pipe and a circulating oil discharging pipe which are communicated with the circulating oil guide pipe in the boiling bed hydrogenation stabilization reactor are arranged outside the boiling bed hydrogenation stabilization reactor, the circulating oil pump discharging pipe is communicated with a circulating oil distributor arranged at the bottom in the reactor, and the expansion rate of a catalyst bed layer is controlled by adjusting the circulating oil amount, and the reaction feeding temperature is controlled. The fluidized bed hydrogenation stabilization reactor is provided with an aged catalyst unloading system and a catalyst supplementing feeding system, and after the initial activity stage of the catalyst without unloading the aged catalyst and adding the supplemented catalyst is passed in the initial operation stage of the device, the bed activity is maintained to be stable by periodically and discontinuously unloading quantitative aged catalyst and adding quantitative supplemented catalyst. The hydrogenation stable working mode of the liquefied oil has the following main disadvantages:
(1) all the coal liquefaction oil is mixed and subjected to hydrogenation stabilization reaction process by adopting the same catalyst, reaction temperature, liquid reaction time and the same catalyst bed expansion ratio, so that the respective optimal hydrogenation stabilization reaction depth-the respective optimal aromatic hydrogenation partial saturation depth of the coal liquefaction oil with different boiling ranges and different aromatic hydrocarbon structures cannot be simultaneously realized;
as can be seen from the fraction yield of Table 1, in the process of hydrogenation stabilization reaction of all coal-liquefied oil mixtures, if the hydrogenation depth of the fraction at the temperature of more than 350 ℃ is optimized, the fraction at the temperature of 200-350 ℃ with the weight flow rate being 1.86 times of that of the fraction is inevitably subjected to excessive hydrogenation saturation, so that the hydrogen supply index of the hydrogenation stabilized oil of the fraction at the temperature of 200-350 ℃ is reduced, and gas is produced more; similarly, if the hydrogenation depth of the fraction at 200-350 ℃ is optimized, the fraction at more than 350 ℃ with the weight flow rate of 0.54 times of the hydrogenation saturation depth is inevitably insufficient, so that the hydrogen supply index of the hydrogenation stable oil of the fraction at more than 350 ℃ is low;
(2) all coal liquefaction oil is mixed in a reaction zone to carry out a hydrogenation stabilization reaction process, metal deposits can not be deposited on certain selected hydrogenation stabilization catalysts in a centralized manner, so that all the hydrogenation stabilization catalysts are polluted by deposited metal, and the deposited metal sulfides such as ferrous sulfide, calcium sulfide, nickel sulfide, fluidized vanadium, sodium sulfide and the like have certain thermal cracking and thermal condensation catalytic effects, so that the reaction activity and the reaction selectivity of the balanced hydrogenation stabilization catalysts are influenced, the occurrence of negative reaction is promoted, the operation condition is worsened, the catalyst aging is accelerated, the catalyst discharging and replenishing quantity is increased, and the catalyst discharging and replenishing quantity operation load is increased; with the improvement of the intensity and the great reduction of the wear rate of the liquefied oil hydrogenation stable catalyst, the replacement period of the catalyst is prolonged, and the quality of the equilibrium catalyst becomes worse and worse because the quantity of deposits such as metal sulfides and coke becomes more and more;
(3) the hydrogenation stabilization reaction process is carried out in one reaction zone by mixing all the coal liquefied oil, and in order to inhibit catalyst coking and bonded particle agglomeration caused by coexistence of coal dust and heavy coal liquefied oil, the volume of the hydrogenation stabilization reactor is increased by adopting a high catalyst bed expansion ratio; in fact, most of the coal liquefaction oil (light distillate) fractionated by the S100 fraction of the atmospheric and vacuum fractionation is light fraction coal liquefaction oil which does not contain coal dust and is lean in higher-order aromatics, so that in a hydrogenation stabilization reaction mode in which all the coal liquefaction oils are mixed, the hydrogenation stabilization reaction process of the light coal liquefaction oil which does not contain coal dust and heavy coal liquefaction oil essentially does not need a high catalyst bed expansion ratio, and a part of the reactor volume formed by the corresponding catalyst bed expansion is ineffective; since a high catalyst bed expansion ratio means that the probability of catalyst particle collision is increased, which leads to faster fragmentation and faster abrasion, the catalyst bed expansion ratio should be reduced as much as possible under the condition of meeting the reaction requirement (forming necessary gaps between catalyst particles to allow coal dust particles to pass freely); particularly, when 2 or more sets of coal hydrogenation direct liquefaction devices are built, the total coal liquefaction oil quantity is large, the raw material coal liquefaction oil quantity in the total hydrogenation stabilization reaction process is large, and the classification hydrogenation stabilization for realizing the optimal hydrogenation stabilization of the coal liquefaction oil with different fractions becomes a necessary choice.
The aim of the invention is to remedy firstly the first drawback deriving from the above-mentioned manner of working, while at the same time ameliorating one or several of the other drawbacks.
The technical principle of the invention is as follows: based on the separated multiple paths of coal liquefaction oil with different distillation ranges, different metal contents and different coal dust contents in the atmospheric and vacuum distillation part S100 of the coal liquefaction generated oil, the classification optimization hydrogenation stabilization reaction is carried out according to the classification centralized processing principle, and meanwhile, a combined hydrogenation stabilization reaction system is adopted, so that the system is simplified, and the investment is reduced.
The basic idea of the invention is: a hydrogenation stabilization method for joint recovery of coal liquefaction oil products with different distillation ranges comprises the steps of respectively introducing heavy fraction coal liquefaction oil rich in high-order aromatic hydrocarbon and light fraction coal liquefaction oil poor in high-order aromatic hydrocarbon into a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, wherein DV1 is a limited expansion bed reaction mode, so that respective optimal hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out, the hydrogen supply index of a hydrogen supply solvent is improved, and the coal liquefaction efficiency is improved; coking materials and metal deposits of high-order aromatic hydrocarbons are concentrated in the catalyst in the DV1, so that the aging and replacement speed of the catalyst in the DV2 can be remarkably reduced; the catalyst replacement speed in DV1 can be increased, and high-quality equilibrium catalyst can be maintained; jointly recovering a hydrogen-rich gas in the DV1 reaction product and the DV2 reaction product and/or jointly recovering a liquid which is rich in hydrogen-supplying hydrocarbon in the DV1 reaction product and the DV2 reaction product; part of the reaction product liquid can be used as the circulating oil of the sub-reaction zone.
The invention has various specific operation modes, different system simplification degrees and different operation characteristics.
The first sub-reaction zone DV1 and the second sub-reaction zone DV2 can be located in different reactors, and can be located in the same reactor.
The invention has an operation mode that based on the increase of the hydrogen supply index of the hydrogen supply solvent of the coal liquefaction oil hydrogenation stable reaction product, the liquefied oil heavy wax oil (the fraction with the conventional boiling range of 480-530 ℃) separated from the oil fractionation part generated by the direct liquefaction of coal hydrogenation is directly used as the solvent oil for preparing the coal oil slurry, and the aromatic hydrocarbon partial hydrogenation saturation is realized in the direct coal liquefaction reaction process without passing through the coal liquefaction oil hydrogenation stable reaction process, so that the organic metal content, the non-liquefied coal dust content, the five-ring and above aromatic hydrocarbon content in the coal liquefaction oil hydrogenation stable reaction feed are greatly reduced, and the coal liquefaction oil hydrogenation stable reaction feed is thoroughly optimized.
The fraction part of the oil generated by direct coal hydrogenation liquefaction usually comprises an atmospheric fractionating tower system and a vacuum fractionating tower system which are operated in series, and when the operation fluctuates, narrow distillate oil discharged from a nearest distillation outlet above a highest boiling point hydrocarbon feed inlet of the atmospheric fractionating tower system carries coal dust, and the narrow distillate oil is introduced into a first sub-reaction zone DV1 to be treated with heavy fraction coal liquefied oil which is rich in high-order aromatics and has high metal content, so that the feeding of the narrow fraction of the low boiling point coal liquefied oil which does not contain the coal dust in the hydrogenation stabilization reaction process can be optimized or improved.
The hydrogen using principle of the invention is that all the new hydrogen in the coal liquefaction oil hydrogenation stabilization reaction process can pass through DV1 or DV2, and can also supply DV1 and DV2 at the same time, but the hydrogen partial pressure in the DV1 reaction process is improved, coking is inhibited, and the hydrogenation speed is improved by recommending that all the new hydrogen in the coal liquefaction oil hydrogenation stabilization reaction process pass through the operation mode of DV1.
The main advantages of the present invention are described below.
Compared with CN112877090A, a coal direct liquefaction circulating solvent and a preparation method and a system thereof, the invention has the main advantages that: the hydrogen-rich gas in the reaction products of different sub-reaction zones is recovered in a combined manner and/or the liquid rich in hydrogen-supplying hydrocarbon in the reaction products of different sub-reaction zones is recovered in a combined manner, so that the process can be simplified and the investment can be reduced.
Compared with the operation mode that all the coal liquefied oil mixed oil uses a single reaction zone boiling bed hydrogenation stabilization reactor, the invention classifies the coal liquefied oil into heavy fraction coal liquefied oil and light fraction coal liquefied oil, and respectively introduces the heavy fraction coal liquefied oil and the light fraction coal liquefied oil into a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, the DV1 is a limited expansion bed reaction mode, and respectively carries out respective optimal hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths, and the invention has the main advantages that:
(1) the coal liquefaction oil with the same distillation range respectively enters different reaction zones, and respective optimal hydrogenation stable reaction depth-respective optimal aromatic hydrocarbon hydrogenation partial saturation depth are realized under different operation conditions, so that the hydrogen supply index of the hydrogenation stable oil is improved and can be improved by 2-4 units or more, and finally, the reaction efficiency of the coal hydrogenation direct liquefaction process using the hydrogenation stable oil is improved, namely, the coal liquefaction rate is improved, and the liquefied oil yield is improved;
(2) coking substances and metal deposits of high-order aromatic hydrocarbons are concentrated in the catalyst in the DV1, so that the aging replacement speed of the catalyst in the DV2 can be obviously reduced, the discharging and replenishing amount of the catalyst is reduced, and the discharging and replenishing operation load of the catalyst is reduced; the catalyst replacement speed in DV2 can be increased, and the high-quality equilibrium catalyst can be maintained;
the equilibrium catalysts in DV1 and DV2 are maintained in a high-activity and high-selectivity state, so that hydrogen consumption can be reduced, gas yield can be reduced, and liquid product yield can be improved, and as the processing scale of the coal liquefied oil hydrogenation stabilizing device is usually large, for example, the processing capacity of the coal liquefied oil hydrogenation stabilizing device for producing 110 ten thousand tons/year of oil is as high as 350 ten thousand tons/year, even if the gas yield is increased by 0.5 weight percent and the liquid yield is reduced by 0.5 weight percent, the absolute value is 1.75 ten thousand tons/year; in other words, the invention can bring great economic benefits;
(3) the hydrogenation stabilization reaction process of the heavy fraction coal liquefied oil rich in high-order aromatics with high metal content is carried out in a reaction zone DV1, and in order to inhibit catalyst coking and bonded particle agglomeration caused by coexistence of coal dust and heavy coal liquefied oil, a high catalyst bed expansion ratio is adopted;
most of coal liquefaction oil (light distillate oil) fractionated by the S100 part of the atmospheric and vacuum fractionation is light fraction coal liquefaction oil without coal dust and poor high-order aromatic hydrocarbon, and hydrogenation stabilization reaction is carried out in an upflow reaction zone (or a reactor) with low catalyst bed expansion ratio, so that the volume of the reactor can be saved, the collision probability of catalyst particles is reduced, and the abrasion speed is reduced; when the production fluctuation of the fractionation part of the upstream coal hydrogenation direct liquefaction device causes the increase of the carrying amount of the unliquefied coal powder of the light fraction coal liquefaction oil, the expansion ratio of the catalyst bed layer in the reaction zone DV1 can be increased by increasing the circulating oil flowing through the reaction zone DV1, so that the coal powder can freely pass through, which is essentially a flushing process, and when the production of the fractionation part of the upstream coal hydrogenation direct liquefaction device is recovered, the quantity of the circulating oil flowing through the reaction zone DV1 is reduced, so that the expansion ratio of the catalyst bed layer in the reaction zone DV1 is recovered to a normal operation state;
(4) under the condition that a hydrogen supply solvent with high hydrogen supply index is produced in the hydrogenation and stabilization reaction process of the coal liquefaction oil, the narrow fraction of the coal liquefaction oil with the highest part or all of organic metal content and the highest boiling range of 5-ring structure aromatic hydrocarbon concentration is directly used as a short-range circulating solvent RDV for preparing the coal oil slurry without passing through the hydrogenation and stabilization reaction process of the coal liquefaction oil, so that the material property of the hydrogenation and stabilization reaction process of the coal liquefaction oil can be greatly improved, and the consumption of the hydrogenation and stabilization catalyst of the coal liquefaction oil is reduced.
When a combined limited expansion bed reactor (DV 1 and DV2 are arranged in one reactor), the hydrogenation stabilization method for joint recovery of different distillation range coal liquefied oil zone reaction products respectively introduces heavy fraction coal liquefied oil rich in high-order aromatic hydrocarbon with high metal content and light fraction coal liquefied oil poor in high-order aromatic hydrocarbon with low metal content into different operation conditions such as catalyst types, liquid residence time, operation temperature, bed expansion ratio, circulation ratio of circulating oil in sub-reaction zones, operation pressure and the like, wherein DV1 is a limited expansion bed reaction mode and carries out respective optimal hydrogenation stabilization reaction at different aromatic hydrocarbon saturation depths, the produced solvent oil can improve coal liquefaction efficiency, liquid products separated from all sub-reaction zone products in a comprehensive separation process are used as circulating oil in the sub-reaction zones, and pure product liquid is separated and fractionated after mixing; coking substances and metal deposits of high-order aromatic hydrocarbons are concentrated in the catalyst in the DV1, so that the aging replacement speed of the catalyst in the DV2 can be remarkably reduced; can accelerate the replacement speed of the catalyst in DV2, maintain high-quality equilibrium catalyst, and maintain high activity and good reaction selectivity.
Several technical solution comparisons similar or analogous to the present invention are as follows:
(1) CN100378201C, having application date of 2005, 07, 15, discloses a method for stabilizing hydrogenation of coal liquefied oil, wherein the coal liquefied oil is filtered, enters a limited expansion bed reactor with hydrogen from the bottom of the reactor, and is contacted with a hydrofining catalyst, and the effluent of the reactor is subjected to gas-liquid separation, fractionation and separation to obtain a product; the hydrogen-rich gas stream separated from the high pressure separator is recycled to the constrained expanded bed reactor. The method adopts the restricted expansion bed reactor, effectively relieves the phenomenon of over-quick pressure drop rise of the reactor, inhibits the over-quick inactivation of the catalyst at the inlet of the reactor, prolongs the start-up period, and simultaneously can remove nitrogen in the coal liquefaction oil and improve the quality of the coal liquefaction oil. According to the method, all coal liquefaction oil is subjected to hydrogenation stabilization reaction together, reactors with internal parallel expansion bed reaction regions for classification treatment of coal liquefaction oil with different properties are not involved, classification treatment of fractions with different properties is not involved, and reactors with internal parallel expansion bed reaction regions are not involved, so that the effect of classification processing of coal liquefaction oil by a single reactor cannot be realized.
(2) CN102433158A, having an application date of 2011, 10, month and 12, discloses a classified hydrogenation saturation method for wide-fraction high aromatic oil, which is used for processing hydrogen-supplying solvent oil for a coal liquefaction reaction process in coal liquefaction oil production, and effectively improves the content of 'effective hydrogen-supplying components' in the hydrogen-supplying solvent oil: the wide-cut high aromatic hydrocarbon oil is fractionated into two fractions to realize the relative separation of double-ring structure aromatic hydrocarbon and multi-ring structure aromatic hydrocarbon in the liquefied oil or realize the relative separation of three-ring structure aromatic hydrocarbon, four-ring structure aromatic hydrocarbon and the above structure aromatic hydrocarbon, then the respective optimal reaction conditions (reaction pressure, catalyst formula, catalyst airspeed, reaction temperature and the like) are selected to carry out aromatic hydrocarbon hydrogenation saturation reaction, and the obtained hydrogenation modified products enter the respective cold high-pressure separation parts respectively. When the quantity of hydrogen-donating solvent oil produced by hydrotreating coal liquefied oil is large and a double-series or multi-series hydrogenation device must be built, the invention also has the effects of reducing device investment, stabilizing operation and enhancing the operation safety of the device. According to the method, fractions with different boiling ranges are subjected to hydro-upgrading reactions in 2 respective independent hydro-upgrading reaction zones, the operating pressure difference is large, coal liquefaction oil with different properties is not classified in different parallel reaction zones of the same reactor, an upflow expansion bed hydro-stabilization reactor is not indicated to be used, a circulating pump conveying circulating oil system is not involved, and therefore the effects of early-stage hydro-stabilization reaction classification processing and later-stage hydro-stabilization reaction combined processing of the coal liquefaction oil with different properties of the single reactor cannot be achieved.
(3) CN107418620B, applied for 2017, 05, month and 15, discloses a processing method of direct coal liquefaction oil and a hydrogen donor solvent. The method comprises the step of carrying out hydrogenation stabilization reaction on fuel oil and direct coal liquefaction oil, wherein the fuel oil is a fraction in coal tar with the distillation range of 150-380 ℃. In the hydrogenation stabilizing reaction of direct coal liquefaction oil, distillate oil (fuel oil) with the distillation range of 150-380 ℃ in coal tar is simultaneously doped. The method completely carries out hydrogenation stabilization reaction on the hydrogenation-stabilized raw oil, does not relate to classification treatment of fractions with different properties, and does not relate to a reactor with an internal parallel expanded bed reaction zone, so that the effect of classifying and processing the coal liquefaction oil by using a single reactor cannot be realized.
(4) CN109022013A, having application date of 2017, 09.06.09, discloses a hydrocracking reaction process and a combined hydrogenation reactor applied to the same, and based on a mature large-scale hydrogenation reactor manufacturing technology, a novel combined coal hydrogenation direct liquefaction reactor and a novel coal liquefaction reaction system are constructed, functions of 2-section or multi-section reaction zones and even a high-pressure separation function of a liquefied product are integrated in different space partitions in one reactor shell, so that the method has the advantages of reducing the number of reactors, enlarging the diameter of the reactor shell, facilitating the arrangement of equipment openings, facilitating manufacturing and maintenance, and enabling the reaction processes to be closely connected, namely shortening the hot material conveying time; it can also be used in the suspension bed hydrogenation reaction process of oil products, especially inferior heavy oil and coal tar. The method relates to a hydrogenation process of liquefied oil obtained in the process of directly liquefying coal to prepare oil by hydrogenation, and is characterized in that:
in a hydrocracking reaction process R10, a conventional liquid hydrocarbon-containing feedstock R10F is converted into a hydrogenated product R10P consisting essentially of hydrogen, conventional gaseous hydrocarbons, conventional liquid hydrocarbons and solids which may be present;
in the thermal high-pressure separation part S1, the hydrogenation product R10P is separated into thermal high-pressure separation gas S1V and thermal high-pressure separation liquid S1L;
a hydrocracking reaction system R10U, using at least one combined hydrogenation reactor CRE, using other reactors and or other hot high-pressure separators, if present;
the combined hydrogenation reactor CRE comprises at least two functional areas, wherein the last functional area is a hydrogenation reaction area or a hot high-pressure separation area, and the other functional areas are hydrogenation reaction areas;
at least two mutually independent spaces VA and VB for different materials to work are divided in a shell CRE-S of the combined hydrogenation reactor CRE;
when the materials flowing between VA and VB are branch materials of homologous materials and the VA and VB are processing areas with the same functions, a parallel operation type 'cluster' reactor is formed;
when the liquid phase materials flowing between VA and VB are in upstream-downstream relation, a series operation type 'sequential' reactor is formed.
The method disclosed in CN109022013A is applied to a hydro-thermal cracking reaction process R10 of parallel operation of homologous materials or upstream and downstream series operation of liquid phase materials, so the catalysts, operating conditions, product targets, and structures of built-in gas-liquid separation zones used in the method are all different from those of the method, and the effects of classification and processing of early-stage hydrogenation stabilization reactions and combined processing of later-stage hydrogenation stabilization reactions of different properties of coal liquefied oil in a single reactor cannot be realized.
(5) CN109722265B, which has application date of 2017, 10 and 27, discloses a direct coal hydrogenation liquefaction reaction process using a reactor with internal parallel reaction zones, which is suitable for reaction processes such as direct coal hydrogenation liquefaction or kerosene co-refining and the like; in an upflow reactor RE, at least 2 parallel reaction zones are divided in a reaction space and respectively receive different liquid materials, products in the parallel reaction zones are mixed to obtain a final product, gas-liquid separation is carried out in a liquid removal space at the top of the RE to obtain a collecting liquid and other products discharged by a collecting cup, and the collecting liquid is circularly supplied to the RE reaction space through a circulating pump; RE can realize the large-scale of 2 parallel small reactors or even 3 small reactors, thereby reducing the number of reactors and saving investment; RE can effectively utilize the total height of the reactors connected in series to form the height superposition of the shell ring, thereby increasing the natural driving force of the liquid circulation system and reducing the pressure difference of the circulation pump; the combined reactor can also be combined with other coal hydrogenation direct liquefaction reactors for use. The method disclosed in CN109722265B is applicable to a direct coal hydrogenation liquefaction reaction process, and therefore, the raw materials, catalysts, operation conditions, reaction types, product targets, cycle oil recycle ratios and the like used in the method are all different from those of the method, and the effects of classification processing of early-stage hydrogenation stabilization reactions and combined processing of later-stage hydrogenation stabilization reactions of coal liquefaction oils with different properties in a single reactor cannot be realized.
(6) CN110819383A of which the application date is 2018, 08 and 14 discloses an inferior hydrocarbon up-flow hydrogenation reaction process using a reactor with internal parallel reaction zones, wherein 2 or more different hydrogenation reaction zones which process the same or different raw materials and have similar operation temperatures are jointly arranged in a combined reactor CRE, so that the number of reactors is reduced, the large-scale reactor is realized, the flow is simplified, and the investment can be saved; in the combined reactor, after products in different reaction areas at the upstream are mixed, deep hydrogenation reaction can be continuously carried out; different reaction zones connected in parallel in the CRE can be connected in series to process 2 or more paths of raw materials in a shunt way, can be positioned at any reactor position in the reaction process, and is particularly suitable for the combined processing of different raw materials such as a hydrogenation thermal cracking reaction process of high carbon residue oil and a mixed processing process of a wax oil hydrogenation modification reaction process after parallel connection; gas-liquid separation can be carried out in the liquid-removing space at the top of the CRE to obtain products such as collecting liquid discharged by the collecting cup, and the collecting liquid can be circularly supplied to an upstream reaction space or supplied to a downstream reaction space through a pressure pump. The method of CN110819383A is characterized in that: in the process of the upflow hydrogenation of the inferior hydrocarbon RU, at least one sub-reaction zone is used for carrying out the hydrogenation thermal cracking reaction RUR of at least one part of the normal boiling point hydrocarbon components higher than 530 ℃ on the inferior hydrocarbon RUF of the normal boiling point hydrocarbon components higher than 530 ℃ to convert the inferior hydrocarbon RUF into the reaction product RUP under the condition that hydrogen, normal liquid hydrocarbon and catalyst possibly exist, and recovering the reaction product RUP; the invention only processes the conventional coal hydrogenation direct liquefaction oil with the boiling point lower than 530 ℃; therefore, the raw materials, catalysts, operation conditions, reaction types, product targets, cycle oil circulation ratios and the like used in the method of CN110819383A are all different from the method essentially, and the effects of classification processing of the early hydrogenation stabilization reaction and combined processing of the later hydrogenation stabilization reaction of the coal liquefaction oil with different properties in the single reactor cannot be realized.
(7) CN112877090A, filed 2021, 01, 15, discloses a coal direct liquefaction circulating solvent and a preparation method and a system thereof, wherein the method comprises the following steps: s1, carrying out a first hydrogenation reaction on the direct coal liquefaction oil to obtain coal liquefaction hydrogenation stabilized oil; performing a second hydrogenation reaction on the coal tar to obtain coal tar hydrogenation stabilized oil; s2, performing first fractionation on the coal liquefied hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c; performing second fractionation on the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e; and S3, mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal liquefaction circulating solvent. According to the invention, the hydrogenated coal tar is introduced to replace part of the coal to directly liquefy the self-produced circulating solvent, so that the stability of the properties of the circulating solvent can be ensured while the performance of the circulating solvent is improved, and the liquefaction and conversion of the coal can be promoted. According to the method, direct coal liquefaction oil and coal tar are respectively treated in 2 independent reactors, and different coal liquefaction oil with different properties is not classified in different parallel reaction zones of the same reactor, so that the effects of classified processing of early-stage hydrogenation stable reactions and combined processing of later-stage hydrogenation stable reactions of the coal liquefaction oil with different properties of the single reactor cannot be realized.
The same method as the invention is not reported
The first purpose of the invention is to provide a hydrogenation stabilization method for jointly recovering different distillation range coal liquefied oil zone reaction products, and jointly recovering hydrogen-rich gas in the reaction products of different sub-reaction zones and/or jointly recovering liquid rich in hydrogen-supplying hydrocarbon in the reaction products of different sub-reaction zones.
The second purpose of the invention is to provide a hydrogenation stabilizing method for jointly recovering reaction products of coal liquefaction oil zones with different distillation ranges, wherein a thermal high-pressure separator for the reaction products of each sub-reaction zone is arranged, and hydrogen-rich gas based on each thermal high-molecular gas is jointly recovered and/or liquid rich in hydrogen-supplying hydrocarbon based on each thermal high-molecular oil is jointly recovered.
The third purpose of the invention is to provide a hydrogenation stabilizing method for jointly recovering reaction products of coal liquefaction oil zones with different distillation ranges, wherein a combined heat high-pressure separator is arranged to carry out gas-liquid separation on the products of different sub-reaction zones in different gas-liquid separation zones, the upper gas phase spaces of different gas-liquid separation zones of the combined heat high-pressure separator are communicated to obtain mixed separated gas, the mixed separated gas leaves the heat high-pressure separator HHPS, and the lower liquid phase spaces of different gas-liquid separation zones of the combined heat high-pressure separator are not communicated to obtain heat high-fraction oil with different properties.
The fourth purpose of the invention is to provide a hydrogenation stabilization method for joint recovery of reaction products of coal liquefaction oil zones with different distillation ranges, wherein the sub-reaction zones DV1 and DV2 are arranged in a pressure-bearing shell of a combined reactor MRE1, the spaces of the DV1 and DV2 are separated, the reaction product DV1-P in the upper space of the DV1 is discharged to leave the combined reactor, and the reaction product DV2-P in the upper space of the DV2 is discharged to leave the combined reactor; all the sub-reaction zone products are separated into hot high-molecular oil and hot high-molecular gas in a hot high-pressure separator HHPS.
The fifth purpose of the invention is to provide a hydrogenation stabilization method for joint recovery of reaction products of coal liquefaction oil zones with different distillation ranges, wherein the sub-reaction zones DV1 and DV2 are arranged in a pressure-bearing shell M1RE of a combined reactor, the upper spaces of the DV1 and DV2 are communicated to form a product mixing zone, and products of all the sub-reaction zones are mixed in the product mixing zone to form a mixed product which leaves the combined reactor MRE2; the mixed product is separated into hot high-pressure oil and hot high-pressure gas in a hot high-pressure separator.
The sixth purpose of the invention is to provide a hydrogenation stabilization method for joint recovery of reaction products of coal liquefaction oil zones with different distillation ranges, wherein the sub-reaction zones DV1 and DV2 are arranged in a pressure-bearing shell MRE3 of a combined reactor, the upper spaces of the DV1 and DV2 are communicated to form a product mixing zone, the products in all the sub-reaction zones are mixed into a mixed product in the product mixing zone, and a liquid collecting cup arranged at the top in the MRE3 and an upper end enclosure of the MRE3 form a gas-liquid separation chamber for separating a circulating liquid and a net reaction product in the sub-reaction zones; the net reaction product is separated into hot high-pressure oil and hot high-pressure gas in a hot high-pressure separator.
The seventh purpose of the invention is to provide a hydrogenation stabilizing method for joint recovery of reaction products of coal liquefied oil zones with different distillation ranges, DV1 and DV2 are arranged in a pressure-bearing shell of a combined reactor MRE3, the upper spaces of DV1 and DV2 are communicated to form a product mixing zone, products in all sub-reaction zones are mixed into a mixed product in the product mixing zone, a liquid collecting cup arranged at the upper part in the MRE3, an upper seal head of the MRE3 and an upper cylinder form a gas-liquid clear separation functional zone, the mixed product is separated into a gas product and clear separated liquid in the clear separation functional zone, part of the clear separated liquid is used as circulating oil in the sub-reaction zone, and the rest of the clear separated liquid is used as a clear liquid product and discharged out of the combined reactor MRE3.
The eighth purpose of the invention is to provide a hydrogenation stabilization method for joint recovery of reaction products of coal liquefied oil zones with different distillation ranges, wherein the sub-reaction zones DV1 and DV2 are arranged in a pressure-bearing shell of a combined reactor MRE3, the upper spaces of the DV1 and DV2 are communicated to form a product mixing zone, the products of all the sub-reaction zones are mixed into a mixed product in the product mixing zone, and a liquid collecting cup arranged at the upper part in the MRE3, an upper seal head of the MRE3 and an upper cylinder form a rapid gas-liquid separation functional zone with short liquid retention time and a slow gas-liquid separation functional zone with long liquid retention time; the fast zone liquid was taken as the circulating liquid and the slow zone liquid was taken as the net liquid product out of the combined reactor MRE3.
Disclosure of Invention
The invention relates to a hydrogenation stabilizing method for joint recovery of different distillation range coal liquefied oil zone reaction products, which is characterized by comprising the following steps of:
the direct coal hydrogenation liquefaction process comprises a direct coal hydrogenation liquefaction reaction process and a fractionation process for generating oil through direct coal hydrogenation liquefaction;
in the direct coal hydrogenation liquefaction reaction process, coal dust and coal oil slurry prepared from a hydrogen supply solvent are converted into a direct coal hydrogenation liquefaction reaction product in the presence of hydrogen and a direct coal hydrogenation liquefaction catalyst;
separating the direct coal hydrogenation liquefaction reaction product to obtain direct coal hydrogenation liquefaction generated oil and hydrogen-rich direct coal hydrogenation liquefaction reaction separated gas;
in the fractionation process of the oil generated by the direct liquefaction of the coal hydrogenation, the oil generated by the direct liquefaction of the coal hydrogenation is separated through a separation process comprising a fractionating tower, so that heavy fraction coal liquefied oil rich in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point of 350-520 ℃ is obtained, and light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point lower than 350 ℃ is obtained;
the low-order aromatic hydrocarbon refers to aromatic hydrocarbon with a monocyclic, bicyclic or tricyclic structure;
the high-order aromatic hydrocarbon refers to aromatic hydrocarbon with four or more ring structures;
the average conventional boiling point of the heavy fraction coal liquefied oil is higher than that of the light fraction coal liquefied oil;
the weight concentration of the high-order aromatic hydrocarbons of the heavy fraction coal liquefied oil is higher than that of the high-order aromatic hydrocarbons of the light fraction coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the light fraction coal liquefied oil is less than 30 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the heavy fraction coal liquefied oil is higher than 70 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil and the light fraction coal liquefied oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain reaction products of the first sub-reaction zone, namely first reaction products DV1-P, and reaction products of the second sub-reaction zone, namely second reaction products DV2-P;
the operation mode of the catalyst bed of the first sub-reaction zone DV1 is a limited expansion bed reaction mode with the expansion rate of the catalyst bed not less than 10%;
the operation mode of the DV2 catalyst bed layer of the second sub-reaction zone is a down-flow fixed bed reaction mode or a limited expansion bed reaction mode;
the limited expansion bed reaction mode refers to that material flow passes through the granular catalyst bed layer in an up-flow mode to enable the granular catalyst bed layer to be in an expansion state, and catalyst particles in the expansion bed reaction zone are not discharged out of the reaction zone under a normal operation state;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P and the hydrogen-containing material flow based on the second reaction product DV2-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction area DV1 and/or the second sub-reaction area DV2 for recycling when at least one part of the hydrogen-rich gas exists or does not exist; and/or, after mixing the hydrogen-donor hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor hydrocarbon material flow based on the second reaction product DV2-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry preparation of the raw material coal oil slurry in the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the presence or absence of a separation liquid resulting from the separation of the second reaction product DV2-P is passed to the first sub-reaction zone DV1.
The first coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are respectively arranged in different reactors;
performing gas-liquid separation on the first reaction product DV1-P and the second reaction product DV2-P in different thermal high-pressure separators in the process of separating and recovering the hydrogenation stable reaction products;
the first reaction product DV1-P is separated into heat high-separation oil HHPS1-L and heat high-separation gas HHPS1-V in a heat high-pressure separator HHPS1, and part of the heat high-separation oil HHPS1-L returns to the first sub-reaction zone DV1; introducing part of the hot high-separation oil HHPS1-L into a second sub-reaction zone DV2 in the presence or absence of the hot high-separation oil HHPS 1-L;
the second reaction product DV2-P is separated into hot high-separation oil HHPS2-L and hot high-separation gas HHPS2-V in a hot high-pressure separator HHPS2, and part of the hot high-separation oil HHPS2-L is returned to the second sub-reaction zone DV2 when part of the hot high-separation oil HHPS2-L exists or does not exist; introducing part of the hot high-separation oil HHPS2-L into a first sub-reaction zone DV;
mixing the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS1-V and the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS2-V, carrying out gas-liquid separation to obtain hydrogen-rich gas, and returning at least part of the hydrogen-rich gas to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 for recycling; and/or the presence of a gas in the gas,
and mixing the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS1-L and the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS2-L, and then carrying out a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid.
The second coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are respectively arranged in different reactors;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the first reaction product DV1-P and the second reaction product DV2-P are separated in a thermal high-pressure separator HHPSM31;
the mode of operation is selected from one of the following:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separation element in the hot high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the hot high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 to be subjected to gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is divided into a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
part of the mixed separation liquid HHPSM32-L returns to the first sub-reaction zone DV1;
returning the partially mixed separated liquid HHPSM32-L to the second sub-reaction zone DV2 in the presence or absence of the liquid;
and (3) type: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the HHPSM33-L, with or without the presence of a portion of the mixed separated liquid, to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
and (5) the following steps: and the second reaction product DV2-P enters a reactor provided with the first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
The third coal liquefaction oil hydrogenation stabilization process comprises the following steps:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE1 and both adopt up-flow reaction, the spaces of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are isolated from each other, reaction products DV1-P of the first sub-reaction zone DV1 are discharged from the first sub-reaction zone DV1 to leave the combined reactor MRE1, and reaction products DV2-P of the second sub-reaction zone DV2 are discharged from the second sub-reaction zone DV2 to leave the combined reactor MRE1;
in the process of separating and recovering the hydrogenation stable reaction product, the first reaction product DV1-P and the second reaction product DV2-P are separated in a hot high-pressure separator HHPSM31, and the operation mode is selected from one of the following modes:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separation element in the hot high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the hot high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 for gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is carried out to obtain a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
returning part of the mixed separation liquid HHPSM32-L to the first sub-reaction zone DV1;
returning the partially mixed separated liquid HHPSM32-L to the second sub-reaction zone DV2 in the presence or absence of the liquid;
and (3) type: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the HHPSM33-L, with or without the presence of a portion of the mixed separated liquid, to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
the 5 th: and the second reaction product DV2-P enters a reactor provided with the first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
The fourth coal liquefaction oil hydrogenation stabilization process comprises the following steps:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE2 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed in the reaction product mixing zone to form a mixed reaction product MRE2-P which leaves the combined reactor MRE2;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the internal space of each separation cylinder is the second sub-reaction zone DV2, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the mixed reaction product MRE2-P is separated into heat high-separation oil HHPSM00-L and heat high-separation gas HHPSM00-V in the heat high-pressure separator HHPSM 00;
part of the hot high-molecular oil HHPSM00-L returns to the first sub-reaction zone DV1;
the existence or nonexistence of part of the hot high-separation oil HHPSM00-L returns to the second sub-reaction zone DV2.
The fifth hydrogenation stabilization process of the coal liquefaction oil comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE3 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE3-P in the reaction product mixing zone;
a liquid collecting cup is arranged at the top in the combined reactor MRE3, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE3 form a gas-liquid separation chamber for separating a collecting liquid of the separation cup and a net reaction product MRE 3-NP;
at least part of the separation cup collection is returned to the first sub-reaction zone DV1;
the presence or absence of a part of the separation cup collection is returned to the second sub-reaction zone DV2;
the net reaction product MRE3-NP is discharged from the combined reactor MRE3;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of the separating cylinders is the second sub-reaction zone DV2, and the space between the separating cylinders and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1.
The sixth hydrogenation stabilization process of the coal liquefaction oil comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE4 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE4-P in the reaction product mixing zone;
the clear gas-liquid separation refers to the separation of a gas-liquid mixture into a gas phase material flow and a liquid phase material flow;
a clear gas-liquid separation type liquid collecting cup is arranged at the top in the combined reactor MRE4, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE4 form a clear gas-liquid separation chamber with a gas-liquid clear separation function;
separating the mixed reaction product MRE4-P into clear collected liquid and a clean reaction product MRE4-NP in a clear gas-liquid separation chamber;
at least part of the clear collected liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a portion of the clear collection liquid is returned to the second sub-reaction zone DV2;
the net reaction product MRE4-NP exits the combined reactor MRE4;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection between the liquid collecting cup and the upper section of the pressure-bearing cylinder section of the combined reactor MRE4 is closed connection, and the space above the bottom plate of the liquid collecting cup is a clear gas-liquid separation zone;
the mixed reaction product MRE4-P below the bottom plate of the liquid collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe positioned in the MRE4 device of the combined reactor passes through the bottom plate of the liquid collecting cup, and a mixed reaction product MRE4-P enters a clear gas-liquid separation area through a liquid guide pipe P61 to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE4-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE4, a liquid guide pipe positioned outside the combined reactor MRE4 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE4 to enter the clear gas-liquid separation zone for gas-liquid separation.
The seventh coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE5 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE5-P in the reaction product mixing zone;
a circulating oil collecting cup and a clean liquid product collecting cup are arranged at the top in the combined reactor MRE5;
the circulating oil collecting cup is a rapid gas-liquid separation functional area with short liquid retention time;
the clean liquid product collecting cup is a slow gas-liquid separation functional area with long liquid retention time;
the fast gas-liquid separation functional area and the slow gas-liquid separation functional area are separated by a separation area partition plate K30, and liquid in the fast gas-liquid separation functional area and liquid in the slow gas-liquid separation functional area are allowed to flow back and forth across the upper edge of the separation area partition plate K30;
part of the mixed reaction product MRE5-P is separated into fast gas and fast liquid in a fast gas-liquid separation functional area;
part of the mixed reaction product MRE5-P is separated into slow gas and slow liquid in a slow gas-liquid separation functional zone;
at least part of the fast-separating liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a part of the fast-separating liquid is returned to the second sub-reaction zone DV2;
at least part of the slowly separating liquid is discharged out of the combined reactor MRE5 as a clean liquid product;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection among the circulating oil liquid collecting cup, the clean liquid product liquid collecting cup and the upper section of the pressure-bearing cylinder section of the combined reactor MRE5 is closed connection, and the space above the bottom plate of the liquid collecting cup is a gas-liquid separation zone; the gas-liquid separation area is divided into a fast gas-liquid separation functional area and a slow gas-liquid separation functional area;
the mixed reaction product MRE5-P below the bottom plate of the circulating oil collecting cup and the clean liquid product collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe P71 positioned in the MRE5 device of the combined reactor passes through a bottom plate of the circulating oil liquid collecting cup and the bottom plate of the clean liquid product liquid collecting cup, and a mixed reaction product MRE5-P enters a gas-liquid separation area through the liquid guide pipe to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE5-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE5, a liquid guide pipe positioned outside the combined reactor MRE5 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE5 to enter the clear gas-liquid separation zone for gas-liquid separation.
The combined hydrogenation stabilization method of the 3 kinds of coal liquefaction oil comprises the following steps:
the method includes the steps that in a fractionation process of the generated oil through direct coal hydrogenation liquefaction, the generated oil through direct coal hydrogenation liquefaction is separated through a separation process including a fractionation tower, and heavy fraction coal liquefied oil rich in high-order aromatics and mainly composed of hydrocarbons with the conventional boiling points higher than 400 ℃, medium fraction coal liquefied oil mainly composed of hydrocarbons with the conventional boiling points of 300-400 ℃ and light fraction coal liquefied oil mainly composed of hydrocarbons with the conventional boiling points lower than 300 ℃ are obtained;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil, the light fraction coal liquefied oil and the medium fraction coal liquefied oil respectively enter a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain a first reaction product DV1-P of the first sub-reaction zone DV1, a second reaction product DV2-P of the second sub-reaction zone DV2 and a third reaction product DV3-P of the third sub-reaction zone; the operation mode of the DV1 catalyst bed layer of the first sub-reaction zone is an ebullated bed reaction mode;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P, the hydrogen-containing material flow based on the second reaction product DV2-P and the hydrogen-containing material flow based on the third reaction product DV3-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 and/or the third sub-reaction zone DV3 for recycling; and/or, after mixing the hydrogen-donor hydrocarbon stream based on the first reaction product DV1-P, the hydrogen-donor hydrocarbon stream based on the second reaction product DV2-P and the hydrogen-donor hydrocarbon stream based on the third reaction product DV3-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry blending of the coal-oil slurry of the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
the presence or absence of a separation liquid obtained by separating the first reaction product DV1-P enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a first sub-reaction zone DV1;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the third reaction product DV3-P to the third sub-reaction zone DV3 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the third reaction product DV3-P with or without the existence enters a first sub-reaction zone DV1;
the presence or absence of a separation liquid obtained by separating the third reaction product DV3-P is fed into the second sub-reaction zone DV2.
The combined hydrogenation stabilization method of the 3 kinds of coal liquefaction oil can be as follows:
the method comprises the following steps that a coal liquefaction oil hydrogenation stabilization reaction process is adopted, and a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE6 and are subjected to upflow reaction.
The operation method of the invention can be as follows:
the method comprises the steps of separating coal hydrogenation direct liquefaction generated oil through a separation process comprising a fractionating tower in a fractionation process of coal hydrogenation direct liquefaction generated oil to obtain heavy fraction coal liquefaction oil and light fraction coal liquefaction oil;
the fractionating process of the coal hydrogenation direct liquefaction produced oil comprises an atmospheric fractionating tower system and a vacuum fractionating tower system which are operated in series, and distillate oil discharged from a nearest distillation outlet above a feeding hole of the highest boiling point hydrocarbon feeding material of the atmospheric fractionating tower enters a first sub-reaction zone DV1 to be jointly treated with the heavy fraction coal liquefaction oil.
The operation method of the invention can be as follows:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, heavy fraction coal liquefaction oil and light fraction coal liquefaction oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, wherein the different operation conditions refer to different one or more of the types of hydrogenation stabilization catalysts, liquid residence time, operation temperature, bed expansion ratio, circulation ratio of circulation oil in the sub-reaction zones and operation pressure, and the method has one or more of the following characteristics:
(1) the pore channel distribution of the hydrogenation stable catalyst carrier of the first sub-reaction zone DV1 has a double-peak characteristic, the peak value of a first pore channel is between 5 and 10 nanometers, and the peak value of a second pore channel is between 10 and 15 nanometers;
(2) the hydrogenation stable catalyst of the first sub-reaction zone DV1 is a mixture of 2 hydrogenation stable catalysts, the pore channel distribution peak value of the carrier of one hydrogenation stable catalyst is between 5 and 10 nanometers, and the pore channel distribution peak value of the carrier of the other hydrogenation stable catalyst is between 10 and 20 nanometers;
(3) the active metal oxide content of the hydrogenation stabilizing catalyst of the first sub-reaction zone DV1 is at least 115% of the active metal oxide content of the hydrogenation stabilizing catalyst of the second sub-reaction zone DV2;
(4) the liquid hourly space velocity of the hydrogenation stable catalyst in the first sub-reaction zone DV1 is not more than 80% of the liquid hourly space velocity of the hydrogenation stable catalyst in the second sub-reaction zone DV2;
(5) the average reaction temperature of the hydrogenation stabilizing catalyst in the first sub-reaction zone DV1 is at least 5 ℃ higher than that of the hydrogenation stabilizing catalyst in the second sub-reaction zone DV2.
The operation method of the invention can be as follows:
the organic metal removal rate of the reaction process of the first time that the heavy fraction coal liquefied oil flows through the first sub-reaction zone DV1 is selected from one of the following: (1) higher than 50%; (2) higher than 70%; (3) higher than 85%.
The operation method of the invention can be as follows:
the expansion rate of a catalyst bed layer of a first sub-reaction zone DV1 for treating the heavy fraction coal liquefied oil is selected from 1 of the following types:
(1) a bubbling bed with an expansion rate of 25-55%;
(2) expanded beds with expansion ratios between 10 and 25%.
The operation method of the invention can be as follows:
the operation mode of the hydrogenation stabilizing catalyst bed layer of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil in the coal liquefied oil hydrogenation stabilizing reaction process is selected from 1 of the following modes:
(1) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 25 to 55 percent of that of a fluidized bed;
(2) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 10-25 percent of that of the expanded bed;
(3) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 0.1-10 percent;
(4) the process medium is operated in a down-flow mode, and the catalyst bed layer is a fixed bed.
The hydrogenation-stabilizing operating conditions of the present invention are typically:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 280-415 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.5-2.0 h -1 Unit weight ofThe chemical hydrogen consumption of the fresh raw material is 0.6-2.5 wt%;
the operating conditions of the second sub-reaction zone DV2 for processing the light-fraction coal liquefied oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 250-405 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.8-2.5 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.5 to 1.7% by weight.
The hydrogenation stabilizing operation conditions of the invention are generally as follows:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 320-400 ℃, and the gas-liquid volume ratio is 200-1000 Nm 3 T, the space velocity of the catalyst volume is 0.9-1.8 h -1 The chemical hydrogen consumption of fresh raw material per unit weight is 0.9-1.7 wt%;
the operating conditions of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 370-390 ℃, and the gas-liquid volume ratio is 200-1000 Nm 3 T, the catalyst volume space velocity is 1.0-2.0 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.8-1.5 wt%.
In general, the average aromatic carbon rate of conventional liquid hydrocarbons having a conventional boiling point higher than 200 ℃ in the entire hydrogenation-stabilized reaction product is 0.35 to 0.42.
In general, the average hydrogen donor index of conventional liquid hydrocarbons having a conventional boiling point above 200 ℃ in the total hydrogenation-stabilized reaction product of the present invention is from 23 to 28.
According to the invention, generally, fresh coal liquefaction oil and circulating oil flow through the first sub-reaction zone DV1, and the weight flow of the circulating oil flowing through the first sub-reaction zone DV1 is 1-5 times of the weight flow of the fresh coal liquefaction oil flowing through the first sub-reaction zone DV1;
fresh coal liquefaction oil and circulating oil flow through the second sub-reaction zone DV2, and the weight flow of the circulating oil flowing through the second sub-reaction zone DV2 is 1-3 times of the weight flow of the fresh coal liquefaction oil flowing through the second sub-reaction zone DV2.
According to the invention, in the coal liquefaction oil hydrogenation stabilization reaction process, the first sub-reaction zone DV1 and the second sub-reaction zone DV2 can be arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of the combined reactor and both adopt up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel, and generally the horizontal cross-sectional area of the first sub-reaction zone DV1 accounts for 30-60% of the horizontal cross-sectional area of the combined hydrogenation reactor.
In the invention, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor and both adopt up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel;
generally, the separation element between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is a cylindrical or regular polygonal cylinder.
The nature of the hydrogenation-stabilising catalyst of the invention may be:
the carrier of the hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 and the carrier of the hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 are both a mixture of alumina and silica, and based on the weight of the carriers, siO 2 The content of the impurity is limited to Na in the range of 2.3 to 2.6 wt% 2 O content of not more than 0.05 wt%, fe 2 O 3 The content is less than or equal to 0.03 weight percent, the content of gibbsite is less than or equal to 3.0 weight percent, the pore volume is 0.9 to 1.35ml/g, and the specific surface area is 300 to 370m 2 /g；
The hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 has the following active metal oxide content based on the weight of the catalyst: WO 3 9.9-15.3 wt% of MoO 3 7.4 to 11.4 weight percent of NiO, 2.3 to 3.6 weight percent of NiO, and B 2 O 3 The content of (B) is 2.1-3.1 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g；
The hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 is, based on the weight of the catalyst,the content of active metal oxides is as follows: WO 3 7.0 to 10.5 weight percent of MoO 3 5.2 to 8.0 weight percent of NiO, 1.6 to 2.5 weight percent of NiO, B 2 O 3 The content of (B) is 1.4-2.2 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g。
The nature of the hydrogenation-stabilising catalyst of the invention may be:
the carrier of the hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 is a mixture of alumina and silica, and the pore distribution characteristics of the carrier are as follows: the proportion of the surface area of the nanometer pore canal lower than 5 to the total pore surface area is 5-10 percent, the proportion of the surface area of the nanometer pore canal between 5 and 10 to the total pore surface area is 30-40 percent, the peak value is between 6.5 and 7.5 nanometers, the proportion of the surface area of the nanometer pore canal between 10 and 15 to the total pore surface area is 30-40 percent, the peak value is between 11.5 and 13.5 nanometers, and the proportion of the surface area of the nanometer pore canal higher than 15 to the total pore surface area is 10-20 percent;
the carrier of the hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 is a mixture of alumina and silica, and the distribution characteristics of the pore channels are as follows: the ratio of the surface area of the nanometer pore canal lower than 5 to the total pore surface area is 10-20%, the ratio of the surface area of the nanometer pore canal 5-10 to the total pore surface area is 70-80%, the peak value is between 6.5-7.5 nanometers, and the ratio of the surface area of the nanometer pore canal higher than 10 to the total pore surface area is 10-20%.
The operation method of the invention can be as follows:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, the expansion rate of a hydrogenation stabilization catalyst bed layer of a first sub-reaction zone DV1 is 25-55%, and the expansion rate of a hydrogenation stabilization catalyst bed layer of a second sub-reaction zone DV2 for treating light fraction coal liquefaction oil is 25-55%.
The operation method of the invention can be as follows:
the preparation solvent of the oil-coal slurry is composed of a short-range circulating solvent RDV and a hydrogen supply solvent with a hydrogen supply index larger than 25.5 from a hydrogenation stable reaction product separation and recovery process; the flow rate of the short-range circulating solvent RDV is 3-20% of the total oil-coal slurry preparation solvent; the average hydrogen supply index of all oil coal slurry preparation solvents is more than 23;
in the fractionation process of the coal hydrogenation direct liquefaction produced oil, the coal hydrogenation direct liquefaction produced oil is separated through a separation process comprising a fractionating tower, so that a first heavy fraction coal liquefied oil mainly composed of hydrocarbon components with the conventional boiling points of 350-490 ℃ is obtained, a second heavy fraction coal liquefied oil containing at least 70 wt% of 5-ring aromatic hydrocarbons in the whole coal liquefied oil and having the average conventional boiling point higher than that of the first heavy fraction coal liquefied oil is obtained, and a light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling points lower than 350 ℃ is obtained;
at least part of the second heavy fraction coal liquefaction oil is used as a short-path circulating solvent RDV for preparing the coal oil slurry without undergoing a coal liquefaction oil hydrogenation stabilization reaction process;
in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-donor-containing hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor-containing hydrocarbon material flow based on the second reaction product DV2-P are mixed and then are subjected to a separation process comprising a fractionating tower to obtain hydrogen-donor-rich hydrocarbon liquid, at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen supply solvent for blending the raw material oil coal slurry in the coal hydrogenation direct liquefaction reaction process, and the hydrogen supply index of the hydrogen supply solvent is more than 25.5.
The operation method of the invention can be as follows:
the method comprises the steps that in the direct coal hydrogenation liquefaction reaction process, the content of inert components in coal powder for preparing the oil-coal-slurry is lower than 10%, and the RDV flow rate of an oil-coal-slurry short-distance circulating solvent is 5-15% of the total oil-coal-slurry preparation solvent.
The operation method of the invention can be as follows:
and secondly, in the hydrogenation stabilization reaction process of the coal liquefaction oil, all new hydrogen enters the reaction zone of the first sub-reaction zone DV1.
Detailed Description
The present invention is described in detail below.
The pressure in the present invention refers to absolute pressure.
The conventional boiling point of the invention refers to the vapor-liquid equilibrium temperature of a substance at one atmospheric pressure.
The conventional boiling ranges referred to herein refer to the conventional boiling ranges of the fractions.
The specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.
The compositions or concentrations or amounts or yield values of the components described herein are weight basis values unless otherwise specified.
The conventional gaseous hydrocarbon refers to hydrocarbon which is gaseous under conventional conditions, and comprises methane, ethane, propane and butane.
The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under conventional conditions, and includes pentane and hydrocarbon with higher boiling point.
The impurity elements in the invention refer to non-hydrogen, non-carbon and non-metal components in the raw oil, such as oxygen, sulfur, nitrogen, chlorine and the like.
The impurity component in the invention refers to the hydrogenation conversion product of non-hydrocarbon component in the raw oil, such as water, ammonia, hydrogen sulfide, hydrogen chloride and the like.
The light hydrocarbon of the invention, which is a naphtha component, refers to a conventional liquid hydrocarbon having a conventional boiling point of less than 200 ℃.
The medium hydrocarbon is a diesel component, and refers to hydrocarbon with a conventional boiling point of 200-330 ℃.
The wax oil component of the present invention refers to hydrocarbons having a conventional boiling point of 330 to 530 ℃.
The heavy hydrocarbon refers to hydrocarbon with a conventional boiling point higher than 330 ℃.
The hydrogen-oil volume ratio refers to the ratio of the standard state volume flow of hydrogen to the volume flow of a specified oil material flow at normal pressure and 20 ℃.
According to the upflow hydrogenation reactor, the macroscopic flow leading direction of a process medium in a reaction space or a hydrogenation catalyst bed layer is from bottom to top.
The limited expansion bed reactor of the invention means that catalyst particles do not leave the main reaction zone along with gas-liquid products in the normal working process, namely do not leave the reactor and do not enter a liquid collecting cup at the top in the reactor; of course, part of the catalyst particles may leave the main reaction zone with the gas-liquid product, i.e. leave the reactor or enter a top liquid collecting cup in the reactor, during a strongly fluctuating abnormal operation; in addition, during normal operation, the small-size crushed particles generated by the collision between catalyst particles, the collision between catalyst particles and the reactor wall, and the collision between catalyst particles and the reactor internals may leave the main reaction zone with the gas-liquid product, i.e. leave the reactor or enter a top collecting cup in the reactor, which is also a reason for arranging a periodic solid particle discharging operation system in the space DV9 below the bottom distribution plate of the restricted expansion bed reactor, and is used for preventing the particle accumulation in the space DV9 from affecting the normal production of the device.
The limited expansion bed reactor is a vertical up-flow reactor, and belongs to an expansion bed catalytic reactor when a catalyst is used; the vertical type means that the central axis of the reactor is vertical to the ground in a working state after installation; the upflow means that the material main body flows from bottom to top in the reaction process and passes through the reaction space or the catalyst bed layer; the expansion bed refers to that a catalyst bed layer is in an expansion state in a working state, the expansion ratio of the catalyst bed layer is defined as the ratio KBED of the maximum height CWH of the catalyst bed layer in the working state when reaction materials pass through and the height CUH of the catalyst bed layer in a standing state when no process fluid passes through, generally, the expansion bed is called a micro-expansion bed when the KBED is lower than 1.10, and the expansion bed is called a boiling bed when the KBED is between 1.25 and 1.55; since the catalyst particles are discharged from the reactor with the process media in either the suspended bed or slurry bed mode of operation, the suspended bed or slurry bed is not a limited expansion bed as described in the present invention.
The back-mixing flow expanded bed reaction zone refers to the operation mode of the reaction zone using the limited expanded bed reactor, wherein liquid flow back-mixing or circulating liquid exists; the return flow or the circulating liquid refers to at least one part of liquid phase XK-L in the intermediate product XK or the final product XK at the flow point K as a circulating liquid flow XK-LR to return to a reaction area at the upstream of the XK, and the reaction product of the circulating liquid flow XK-LR flows through the point K and exists in the XK. The mode of forming the back flow can be any suitable mode, such as arranging a built-in inner circulation tube, a built-in outer circulation tube, a built-in liquid collecting cup, a flow guide tube, a circulating pump, an external circulating tube and the like.
The liquid collecting cup or the liquid collector arranged in the reactor refers to a container which is arranged in the reactor and is used for collecting liquid, the upper part or the upper side surface is usually opened, and the bottom part or the lower side surface is provided with a guide pipe for discharging the collected liquid; the top liquid collector of the limited expansion bed reactor is usually arranged in a liquid removal area of gas-liquid materials to obtain mixed-phase material flow of liquid and gas-liquid or obtain liquid and gas.
The structure form of the limited expansion bed reactor can be any suitable form, and the working mode of the bed layer of the sub-reaction zone can be plug flow or return flow with internal circulation.
The circulating liquid of the limited expansion bed reactor can come from an overhead collecting cup in the reactor, is particularly suitable for a device with large raw oil scale, can form an internal pump type circulating system by using an internal liquid collecting guide cylinder and a built-in circulating pump arranged in the reactor, and can form an external pump type circulating system by using an external circulating pump with an internal liquid collecting guide cylinder and a circulating pump arranged outside the reactor.
The circulating liquid of the limited expansion bed reactor can come from a liquid phase region of a thermal high-pressure gas-liquid separator of an expansion bed reaction product at the downstream of the limited expansion bed reactor, and is particularly suitable for a device with smaller raw oil scale.
The limited expansion bed reactor of the invention has the following working modes:
(1) a bubbling bed with an expansion rate of 25-55%;
(2) a low expansion bed having an expansion ratio of 10 to 25%;
(3) a micro-expanded bed with an expansion rate of 0.5-10%.
The limited expansion bed reactor of the invention can work in a way of intermittently discharging the catalyst with reduced activity from the bottom of the bed layer and intermittently supplementing fresh catalyst from the upper part of the bed layer so as to maintain the stable inventory and the stable activity of the catalyst in the bed layer.
The thermal high separator refers to a gas-liquid separation device for separating intermediate products or final products of hydrogenation reaction.
The hydrogen-donating hydrocarbon is described below.
The hydrogen donor hydrocarbon refers to a hydrocarbon component with a hydrogen donor function in the direct coal hydrogenation liquefaction reaction process, and the hydrogen donor hydrocarbon comprises partially saturated bicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons, and is an ideal component of the hydrogen donor solvent oil used in the direct coal hydrogenation liquefaction process. In the hydrogen donor, the hydrogen donor speed of the dihydro body is higher than that of the tetrahydro body, and the hydrogen donor speed of the dihydro body of the tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of the bicyclic aromatic hydrocarbon; tests have demonstrated that polycyclic aromatic hydrocarbons, although not having a hydrogen donating ability, have the ability to transfer hydrogen. The relative hydrogen supply rates at 400 ℃ for the following components were as follows:
the direct coal liquefaction process, which includes the coal hydrogenation direct liquefaction process and other direct coal liquefaction processes, is described in detail below.
The direct coal liquefaction process of the invention refers to a method for directly obtaining hydrocarbon liquid by treating coal, and can be divided into the following processes according to the difference of solvent naphtha and catalyst, the difference of pyrolysis mode and hydrogenation mode and the difference of process conditions:
(1) a dissolution pyrolysis liquefaction method: extracting coal by pyrolysis with heavy solvent to obtain low ash extract (bentonite); the oil mainly comprising heavy oil can be obtained by extracting with light solvent under supercritical condition. The method does not use hydrogen, the yield of the former process is high but the product is still solid, and the extraction rate of the latter process such as a supercritical extraction (SCE) method is not too high;
(2) solvent hydrogenation extraction liquefaction method: if solvent refining coal methods I and II (SRC-I and SRC-II), a hydrogen supply solvent method EDS, a Japan New energy development organization liquefaction method (NEDOL) and the like are adopted, hydrogen is used, but the pressure is not too high, and the solvent naphtha has obvious effect;
(3) high pressure catalytic hydrogenation: such as the new and old liquefaction processes in Germany (IG and NewIG) and the hydrogen-Coal process in the United states (H-Coal) belong to this class;
(4) coal and residual oil combined processing (co processing): oil-coal co-refining refers to co-processing of coal and non-coal derived oil at the same time, and usually residual oil is used as solvent oil to pass through a reactor together with coal once, without circulating oil. The residual oil is simultaneously subjected to hydrocracking to be converted into light oil. The united states, canada, germany, and the soviet union have different processes;
(5) underground liquefaction method: injecting a solvent into the underground coal seam to depolymerize and dissolve the coal, adding the impact force of a fluid to collapse the coal, suspending the incompletely dissolved coal in the solvent, pumping the solution by a pump, and separating and processing the solution;
(6) a dry distillation liquefaction method: the coal is pyrolyzed to obtain tar, and then the tar is subjected to hydrocracking and quality improvement.
The direct coal hydrogenation liquefaction process is a method for coal hydrogenation liquefaction in the presence of solvent oil, wherein the solvent oil can be hydrogen supply solvent oil with improved hydrogen supply capacity in a hydrogenation stabilization process or solvent oil without being modified in the hydrogenation stabilization process, and various processes such as the following processes are available according to the difference of the solvent oil and the catalyst and the difference of hydrogenation process conditions:
(1) solvent hydrogenation extraction liquefaction method: if solvent refining coal methods I and II (SRC-I and SRC-II), a hydrogen supply solvent method EDS, a Japan New energy development organization liquefaction method (NEDOL) and the like are adopted, hydrogen is used, but the pressure is not too high, and the solvent naphtha has obvious effect;
(2) high pressure catalytic hydrogenation: such as the old and new liquefaction processes in Germany (IG and NewIG) and the hydro-Coal process in the United states (H-Coal) belong to this category;
(3) coal and residual oil combined processing (co processing): residual oil is used as solvent oil and passes through the reactor together with coal at one time without circulating oil; residual oil is subjected to hydrocracking at the same time and is converted into light oil; the united states, canada, germany, and the soviet union have different processes;
(4) a direct coal liquefaction method of Shenhua group in China;
(5) the patent CN100547055C discloses a thermosol catalytic method for preparing liquid fuel by using lignite, belonging to the lignite medium-pressure hydrogenation direct liquefaction process, including two processes of coal liquefaction reaction process and coal liquefaction oil hydrogenation modification process. In order to improve the conversion rate of direct coal liquefaction and realize that coal raw materials enter a coal liquefaction reactor, coal is usually made into coal powder before entering the coal liquefaction reactor, the coal powder is mixed with solvent oil with good hydrogen supply capacity to prepare coal oil slurry, and the coal oil slurry enters the coal liquefaction reactor after being pressurized and heated.
In the direct coal hydrogenation liquefaction process, no matter what kind of direct coal hydrogenation liquefaction process, the goal is to obtain oil products, the sought function is coal-to-oil, the necessary chemical change is coal hydrogenation, the common characteristic of the prior art is to use solvent oil and catalyst, the conventional boiling range of the solvent oil is generally 200-530 ℃, most 200-450 ℃, the best is 265-430 ℃, most of the solvent oil is distilled oil or hydrogenation modified oil thereof, and most of the contained aromatic hydrocarbon is aromatic hydrocarbon with 2-4 ring structures. Therefore, no matter what kind of coal hydrogen direct liquefaction process, the produced external oil discharge or coal liquefaction oil (usually coal liquefaction light oil) or coal liquefaction oil modified oil can be processed in the high aromatic hydrocarbon hydrogenation thermal cracking reaction process BR by using the method provided by the invention as long as the composition of the external oil discharge or coal liquefaction oil (usually coal liquefaction light oil) or coal liquefaction oil modified oil has the raw material composition characteristics of the invention.
The direct coal hydrogenation liquefaction process is a hydrogenation liquefaction reaction process in which coal and molecular hydrogen which may exist are used as raw materials, a specific oil product (usually, hydrogenation modified oil of coal liquefaction oil) is used as hydrogen supply solvent oil, and under certain operation conditions (such as operation temperature, operation pressure, solvent oil/coal weight ratio, hydrogen/solvent oil volume ratio and a proper hydrogenation catalyst), the coal directly undergoes carbon-carbon bond thermal cracking, free radical hydrogen addition stabilization and the like.
The direct coal hydrogenation liquefaction oil refers to an oil product produced in the coal hydrogenation liquefaction reaction process, exists in the effluent of the coal hydrogenation liquefaction reaction, and is a comprehensive reaction product based on hydrogen supply solvent oil, reaction consumed coal and reaction transferred hydrogen.
After the coal hydrogenation direct liquefaction reaction process is normally operated, the hydrogen-supplying solvent oil is generally hydrogenated modified oil of coal liquefied oil (usually distillate oil with a conventional boiling range higher than 165 ℃) produced in the coal hydrogenation liquefaction reaction process, and the main goal of the coal liquefied oil hydrogenation modification process is to produce the solvent oil for the coal hydrogenation direct liquefaction reaction process, specifically, to improve the content of components with good hydrogen supply function in oil products, such as naphthenic benzenes and dicycloalkylbenzenes, and the coal liquefied oil hydrogenation modification process is a hydrogenation process with moderate aromatic hydrocarbon saturation based on the fact that the coal liquefied oil contains a large amount of bicyclic aromatic hydrocarbons and a large amount of tricyclic aromatic hydrocarbons.
The final goal of the coal liquefaction reaction process is to produce an oil product for external supply, and usually, the hydrogenated modified oil produced in the coal liquefied oil hydrogenation modification process is divided into two parts: one part is used as hydrogen supply solvent oil for the coal liquefaction reaction process, and the other part is used as external oil discharge in the coal liquefaction oil preparation process. Usually, at least a part of coal liquefaction light oil generated in the coal liquefaction reaction process is used as external oil discharge A in the coal oil preparation process, the rest of the coal liquefaction oil is used as raw oil in the coal liquefaction oil hydrogenation modification process to produce hydrogen supply solvent oil and external oil discharge B for the coal liquefaction reaction process, at this time, two paths of external oil discharge A and B exist, and the final outward oil discharge directions of the two paths of external oil discharge A and B are both generally used for producing high-quality oil products such as diesel oil fractions and naphtha fractions through a deep hydrogenation upgrading process.
In the direct coal hydrogenation liquefaction reaction process, a hydrogen supply solvent is essentially the most main foreground catalyst for the positive and negative reactions of coal liquefaction, rapidly provides most of active hydrogen in the coal liquefaction process, and directly determines the rapid hydrogenation stable speed of pyrolysis free radical fragments, so that the thermal condensation reaction is inhibited; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite, molybdenum sulfide and the like are more similar to a retarder of coal liquefaction negative reaction in nature, and solid catalyst particles adsorb colloid and asphaltene molecules MK with high viscosity, and the MK is contacted with active hydrogen on the surface of the solid catalyst, so that the thermal shrinkage of the MK is inhibited; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite, molybdenum sulfide and the like are essentially simultaneously used as a recovery catalyst of a hydrogen donor dehydrogenation product SH-Z, solid catalyst particles adsorb SH-Z and enable SH-Z to be in contact with active hydrogen on the surface of the solid catalyst, so that hydrogenation is recovered into hydrogen-supplying hydrocarbon with hydrogen supply capacity, and the recovery speed of the hydrogen donor dehydrogenation product SH-Z is directly determined; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite and the like are basically and simultaneously weak catalysts for target hydrocracking reactions such as the hydrocracking of asphaltene and preasphaltene. Therefore, in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite and molybdenum sulfide are more like a catalyst operating in a background in a certain sense, and play a supporting and promoting role in coal liquefaction target product distillate oil. In the reaction process of preparing the oil by coal hydrogenation, the function of the hydrogen donor solvent DS is very important, so the operation condition and the effect of the hydrogenation stabilization reaction process of the solvent oil are naturally very important.
The oil product obtained by directly liquefying coal through hydrogenation comprises naphtha (the fraction with the conventional boiling range of 60-180 ℃), first light diesel oil (the fraction with the conventional boiling range of 180-220 ℃), second light diesel oil (the fraction with the conventional boiling range of 220-265 ℃), heavy diesel oil (the fraction with the conventional boiling range of 265-350 ℃), light wax oil (the fraction with the conventional boiling range of 350-480 ℃), heavy wax oil (the fraction with the conventional boiling range of 480-530 ℃), and liquefied residual oil (hydrocarbons with the conventional boiling point higher than 530 ℃).
Naphtha (fraction having a conventional boiling range of 60 to 180 ℃) in the coal liquefaction product is a target product fraction, and if necessary, it is subjected to deep hydrofining such as desulfurization and denitrification, and it is generally desirable that hydrogenation saturation of benzene rings is caused as little as possible.
The first light diesel oil (the conventional fraction with the boiling range of 180-220 ℃) in the coal liquefaction product is not suitable for entering the coal hydrogenation direct liquefaction reaction process, because the boiling point is too low, the first light diesel oil is easy to vaporize and can not be used as a liquid phase solvent component; if the coal is subjected to the direct coal hydrogenation liquefaction reaction process, the products of the further thermal cracking reaction generate a large amount of gas and are not economical; therefore, unless the value of the gas hydrocarbon is huge, the first light diesel oil is generally not suitable to be processed in a direct coal hydrogenation liquefaction reaction process or a special hydrocracking process or a hydrocracking process or other thermal cracking processes, and can be generally subjected to a hydrofining reaction process for desulfurization and denitrification to produce clean light diesel oil.
In addition, in the direct coal hydrogenation liquefaction process, the second light diesel oil or the hydrogenation stabilized oil thereof plays a role of a liquid phase basic solvent component in the front reaction process of the direct coal hydrogenation liquefaction reaction process, but most of the second light diesel oil or the hydrogenation stabilized oil thereof is vaporized in the rear reaction process of the direct coal hydrogenation liquefaction reaction process, and the second light diesel oil or the hydrogenation stabilized oil thereof usually has surplus resources in the direct coal hydrogenation liquefaction reaction process, so the second light diesel oil or the hydrogenation stabilized oil thereof belongs to a main product of the direct coal hydrogenation liquefaction reaction process, and therefore, part of the second light diesel oil or the hydrogenation stabilized oil thereof in the coal hydrogenation liquefaction product is usually used as the light hydrogen supply solvent oil for the direct coal hydrogenation liquefaction reaction process, and part of the second light diesel oil or the hydrogenation stabilized oil thereof is used as a hydrogenation upgrading raw material for producing a final product in the hydrogenation upgrading reaction process.
In addition, in the direct coal hydrogenation liquefaction process, the heavy diesel oil or the hydrogenation stabilized oil thereof plays a role of a liquid phase basic solvent component in the whole flow of the direct coal hydrogenation liquefaction reaction process, and usually has residual resources in the direct coal hydrogenation liquefaction reaction process, so the heavy diesel oil or the hydrogenation stabilized oil thereof belongs to a main product in the direct coal hydrogenation liquefaction reaction process, therefore, part of the heavy diesel oil or the hydrogenation stabilized oil thereof is usually used as the heavy hydrogen supply solvent oil for the direct coal hydrogenation liquefaction reaction process, and part of the heavy diesel oil or the hydrogenation stabilized oil thereof is used as a hydrogenation quality-improving raw material for the hydrogenation quality-improving reaction process to produce a final product.
In addition, in the direct coal hydrogenation liquefaction process, the light wax oil or the hydrogenation stabilized oil thereof plays a role of a liquid phase basic solvent component at the last high-temperature stage of the direct coal hydrogenation liquefaction reaction process and is usually a scarce resource which is difficult to balance per se in the direct coal hydrogenation liquefaction reaction process, so that the light wax oil or the hydrogenation stabilized oil thereof which is a coal liquefaction product is usually completely used as the heavy hydrogen supply solvent oil for the direct coal hydrogenation liquefaction reaction process, and simultaneously hydrogenation thermal cracking reaction required in the light coal liquefaction process is carried out.
Heavy wax oil (fraction with a conventional boiling range of 480-530 ℃) in coal liquefaction products, the process of converting heavy wax oil (fraction with a conventional boiling range of 480-530 ℃) into light materials containing solid particles and seriously lacking hydrogen needs to be carried out under a liquid phase condition which is rich in hydrogen-supplying hydrocarbon and can provide a large amount of active hydrogen atoms, so that the materials cannot be rapidly coked to maintain the long-period operation of the device, the dispersion of the coal liquefaction heavy wax oil in the liquid phase in a reactor also needs to be carried out by means of the dispersion and dissolution of a large amount of hydrogen-supplying hydrocarbon, and a thermal condensation compound or a coking substance of the coal liquefaction heavy wax oil needs to be dispersed and carried out of a reaction space by taking liquefied semicoke as an aggregation carrier, so that the deep conversion of the coal liquefaction heavy wax oil in the direct coal hydrogenation liquefaction reaction process is a reasonable inevitable choice, or the deep conversion of the hydrogenation stable oil obtained by the coal liquefaction heavy wax oil in the direct coal hydrogenation reaction process is a reasonable inevitable choice; in addition, for the direct coal hydrogenation liquefaction process, the heavy wax oil or the hydrogenation stabilized oil thereof plays a role of a liquid phase basic solvent component at the last high-temperature stage of the direct coal hydrogenation liquefaction reaction process, and is usually a scarce resource which is difficult to balance in the direct coal hydrogenation liquefaction reaction process, so that the heavy wax oil or the hydrogenation stabilized oil thereof which is a coal liquefaction product is usually completely used as the heavy hydrogen supply solvent oil to be used in the direct coal hydrogenation liquefaction reaction process, and meanwhile, the hydrogenation thermal cracking reaction required in the light coal liquefaction process is carried out.
Because the hydrocarbons with the conventional boiling point higher than 530 ℃, namely the liquefied residual oil, in the coal liquefaction product exists in the coal liquefaction residue stream at the bottom of the vacuum distillation tower, the hydrocarbons, namely the liquefied residual oil, are usually discharged out of the system and are not recycled, and certainly, part of the hydrocarbons can be recycled as required.
The atmospheric and vacuum distillation part S100 of the oil generated by the direct liquefaction of coal by hydrogenation in the existing direct coal liquefaction process is described below.
Taking a unique set of commercial 100-million-ton/year coal hydrogenation direct liquefaction device owned by the coal oil preparation company of shenhua-erdos, china as an example, the oil (hot medium oil, warm medium oil and cold medium oil) generated by the direct coal hydrogenation liquefaction enters an atmospheric and vacuum fractionation part S100; s100 is provided with a coal slurry atmospheric fractionating tower C-301, a coal slurry vacuum fractionating tower C-302 and auxiliary systems thereof to recover coal liquefaction distillate oil and bottom oil residue of the vacuum fractionating tower, and the process aims are as follows: (1) recovering all coal liquefaction distillate oil and sending the coal liquefaction distillate oil to a hydrogenation stabilizing device to be used as hydrogenation stabilizing feeding; (2) performing solid-liquid separation in a reduced pressure fractionating tower C-302 to separate out all solid particles such as unconverted coal, ash and catalyst to be used as reduced pressure residue, wherein the solid content of the oil residue at the bottom of the reduced pressure fractionating tower is 50wt%; see document a01: (1) publication name: direct coal liquefaction process and engineering, pages 197, 212 to 213, and 226 to 229; (2) encoding a search graph: ISBN encoding: 9-78703-04308-23; (3) and (3) compiling: wu Xiu Chao, shu Gong Ping, li Ke Jian and Xishun Ming; (4) the publishing company: scientific press.
The process of the atmospheric and vacuum distillation part S100 is as follows:
(1) the atmospheric fractionating tower C-301 has three feed inlets, one is the heavy slurry oil feed with 407 deg.C from the hot middle separator D-205; the other is that the light oil with 204 ℃ from the medium-temperature medium-pressure separator D-206 directly enters the upper section of the atmospheric fractionating tower, and the cold medium-separated oil from the cold medium-pressure separator D-207 is used as the top reflux;
the operating pressure of the atmospheric fractionating tower C-301 is 0.2MPa (a), and the tower top temperature is 105 ℃; the oil from cold medium pressure separator D-207 was heated to 118.9 ℃ by steam heater 103-E-302 as reflux to the top of the column. Condensing and cooling the tower top gas to 40 ℃ by a water cooler E-301, and feeding the cooled tower top gas into a normal overhead tank D-301; removing light hydrocarbon from gas separated from the atmospheric overhead tank to recover the light hydrocarbon, and using light liquefied oil at the bottom of the tank as the feed of the T-STAR device; the first side of C-301 is 149.5 ℃ light distillate, used as T-STAR unit feed; the second side of C-301 is 258.1 ℃ Atmospheric Gas Oil (AGO) which is used as the feed to the T-STAR unit; the third side line is 329.4 ℃ Heavy Atmospheric Gas Oil (HAGO), one part of the heat-exchanged gas oil is returned to the atmospheric fractionating tower after being subjected to heat exchange by a steam generator E-304, one part of the heat-exchanged gas oil is divided into two parts after being filtered by a filter S-301A/B, one part of the heat-exchanged gas oil is returned to the lower section of the bottom of the C-301 tower to be used as flushing oil of heavy oil feeding, and the other part of the heat-exchanged gas oil is used as feeding of a T-STAR device; three side lines of the atmospheric fractionating tower C-301 are extracted, the fractionating precision is not required, and the tower tray is mainly used as a heat exchange tower tray; all feeds to the T-STAR removal unit are eventually combined together; when the T-STAR device is not started, the original feeding material to the device is changed into a coal-to-liquid distillate oil air cooler A-304 to be cooled and then is sent to a heavy liquefied oil tank area;
in order to prevent the deposition and coking of the solid at the bottom of the atmospheric fractionating tower C-301, the bottom of the atmospheric fractionating tower is designed into a conical bottom, and a circulating oil coal slurry at the bottom of a tower is maintained by a tower bottom pump P-307A/B/C to stir the oil coal slurry at the bottom of the tower;
(2) pumping the oil coal slurry at the bottom of the atmospheric fractionating tower by a tower bottom pump P-307A/B/C, heating the oil coal slurry to 406 ℃ in a feeding heating furnace F-302 of a reduced pressure fractionating tower, and then feeding the oil coal slurry into the reduced pressure fractionating tower C-302; the vacuum fractionating tower is set up for the main purpose of realizing the liquid-solid separation under reduced pressure, ensuring the solid content at the bottom of the tower to reach 50wt%, and preventing the solid from being carried into the distillate oil at the vacuum side line as much as possible;
the vacuum fractionating tower C-302 is provided with three side lines, the first side line is light reduced pressure gas oil (LVGO), the LVGO is pumped out by a pump P-310A/B at 154.5 ℃, part of the LVGO is cooled to 54 ℃ in an air cooler A-303, the LVGO returns to the vacuum fractionating tower to be used as top reflux after being filtered by a filter 103-S-302A/B, and the rest LVGO is sent to a T-STAR device feeding main pipe; the second side line is Heavy Vacuum Gas Oil (HVGO), which is pumped out by a pump P-311A/B at 276.8 ℃, part of the heavy vacuum gas oil is returned to the vacuum fractionating tower as middle-stage reflux after heat exchange in a steam generator E-306 to 190 ℃ and filtration in a filter S-304A/B, and the rest HVGO is sent to a feeding main pipe of a T-STAR device; another strand of oil is separated from an HVGO extraction pump P-31lA/B, and is separated into three strands after passing through a filter S-304A/B, and the three strands of oil are respectively used as washing oil to return to the lower section of the reduced pressure fractionation tower; the third side line is the vaporized oil, which is pumped out by a pump P-312A/B at 305 ℃, one part of the vaporized oil returns to the front of the vacuum fractionating tower feeding heating furnace for heat extraction and then returns to the bottom of the vacuum fractionating tower for heating, and the other part returns to the third side line oil collecting tank for circulation; the vacuum fractionating tower is provided with a three-stage vacuum pumping system, and the pressure at the top of the tower is kept below 2kPa (a); the reduced-overhead oil is pumped out of the reduced-overhead liquid separation tank D-302 by a pump P-309A/B and is converged with the normal-overhead light liquefied oil to be used as the feed of the T-STAR device;
in order to prevent the deposition and coking of the solid at the bottom of the C-302 tower of the vacuum fractionating tower, the C-302 tower is also designed to be provided with a conical bottom; the slag reduction of the C-302 tower bottom containing 50% of solids is pumped out by a vacuum fractionating tower bottom pump P-315A/B/C, a strand of circulating residual oil with C-302 removed is led out from the pump outlet, so as to achieve the effect of stirring the C-302 tower bottom oil, and the circulating residual oil can also be returned to the vacuum fractionating tower after being largely circulated by an oil residue forming device; the rest slag reduction is processed by an oil slag forming device; if the residual oil forming device is not started or fails, the vacuum oil slurry mixing pump P-424A/B mixed with the solvent is used for mixing, cooling and diluting the mixture, and then the mixture is sent to a solid heavy oil-containing sump oil tank in a tank area.
In the atmospheric and vacuum distillation part S100, in a fractionating tower system, the distillation range and the density of the distillate oil discharged from the lower distillation outlet are higher than those of the distillate oil discharged from the upper distillation outlet; in the atmospheric fractionating tower C-301 and the coal slurry reduced pressure fractionating tower C-302, distillate oil discharged from a distillation outlet most adjacent to the upper part of the heaviest distillation range feeding material contains a certain coal component, and the content of the coal powder can be increased when the operation fluctuates, so that the operation mode of the coal liquefied oil hydrogenation stabilizing reactor is limited, the blockage of a particle catalyst bed layer is prevented, the long-term continuous operation is ensured, and the coal liquefied oil hydrogenation stabilizing reactor adopts a fluidized bed reactor mode; the fraction S100 is fractionated under atmospheric pressure and reduced pressure, and the distillate oil with a high distillation range contains more organic metal than the distillate oil with a low distillation range.
Table 3 lists some of the aromatic components present in the coal liquefaction oil and their comparative hydride boiling point, condensation point and density data to illustrate the variation of typical aromatic components from comparative hydride boiling point, condensation point and density, specifying the boiling point of the hydrogen donating hydrocarbon.
For the hydrogenation to stabilize the hydrocarbon components in the reaction feed coal liquefaction oil, the boiling point data set forth in table 3 suggests that: referring to the conventional boiling point (278 ℃) of acenaphthene, the conventional boiling point (340 ℃) of anthracene and the conventional boiling point (450 ℃) of tetracene, taking 260 ℃, 370 ℃ and 450 ℃ as boundary points, the fraction with the conventional boiling point lower than 260 ℃ contains a large amount of aromatic hydrocarbons with a mono-ring structure and a bi-ring structure, the fraction with the conventional boiling point of 260-370 ℃ contains a large amount of aromatic hydrocarbons with a di-ring structure and a tri-ring structure, the fraction with the conventional boiling point of 370-450 ℃ contains a large amount of aromatic hydrocarbons with a tri-ring structure and a tetra-ring structure, and most of the aromatic hydrocarbons with a pentacene structure and more rings are concentrated in the fraction with the conventional boiling point higher than 450 ℃.
TABLE 3 summary of typical aromatic components and their comparative hydride boiling points, condensation points and densities
The process for the hydro-stabilization of coal liquefaction oil is described in detail below.
The primary purpose of the hydrogenation stabilization process of the coal liquefaction oil is to prepare qualified solvent oil for a direct coal liquefaction unit, and meanwhile, shallow hydrofining is performed on the components of the light liquefaction oil, so that most of S, N, O, metal and other heteroatoms are removed, and a stable raw material can be provided for a downstream hydrogenation modification device; and the continuous operation is maintained by adapting to the fluctuation of the coal dust content of the coal liquefied oil.
The hydrogenation stabilization reaction of the coal liquefaction oil is mainly divided into three types, namely olefin hydrogenation saturation reaction, hydrogenation heteroatom removal reaction and partial hydrogenation saturation reaction of partial aromatic ring.
The most core function of the hydrogenation stabilization reaction of the coal liquefaction oil is to provide a qualified hydrogen supply solvent for the coal hydrogenation direct liquefaction device, and the main source of the hydrogen supply of the solvent is the hydrogen supply capacity of a moderately partially hydrogenated and saturated aromatic ring conversion product, namely a partially saturated ring in a two-ring or polycyclic aromatic hydrocarbon structure.
The main target reaction of the hydrogenation stabilization of the coal liquefaction oil is to saturate one or more benzene rings of bicyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon and simultaneously reserve one or more benzene rings, so that the coal liquefaction oil has aromaticity and can provide active hydrogen; the ring which is most easy to hydrogenate and is stable in bicyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon is the ring with the lowest aromaticity.
Therefore, the aromatics hydrogenation saturation activity of the coal liquefaction oil hydrogenation stabilization catalyst is important and should be determined according to specific situations. The aromatic carbon rate f before and after the hydrogenation stabilization reaction of the coal liquefaction circulating solvent is generally considered a Rate of change (Δ f) a ) The hydrogen supply capability of the circulating solvent is strongest at 0.07-0.10, that is, the ideal index of the reaction depth of the general coal liquefaction oil hydrogenation stabilization is as follows: the aromatic carbon rate of the hydrogen-donating solvent is reduced by 0.07-0.1 compared with that of the coal liquefied oil.
A hydrogenation stable catalyst for coal liquefied oil is generally composed of at least one VIB group metal component and at least one VIII group metal component, commonly used bimetallic components are Co-Mo, ni-Mo and Ni-W, commonly used trimetal components are Ni-Mo-W, co-Ni-Mo and the like; the optimal hydrogenation stabilizing catalyst formula (active metal component, content proportion, carrier property and proportioning scheme) of the specific coal liquefied oil needs to be determined according to the specific coal liquefied oil composition and the hydrogenation stabilizing reaction target.
The fluidized bed coal oil hydrogenation stabilizing catalyst has metal oxide content of 15-30 wt%, usually 20-27 wt%.
When the light fraction coal liquefied oil is subjected to hydrogenation stabilization by adopting a layered catalyst bed, 2 or more hydrogenation stabilization catalysts can be used in series
The coal liquefied oil hydrogenation stabilizing catalyst can be added with a modifying component such as boron according to the active metal, and the carrier of the catalyst can be alumina or a mixture of the alumina and silica, and is added with the modifying component such as phosphorus.
Due to the fact that the aromatic hydrocarbons with different ring numbers have different molecular sizes and different hydrogenation saturation reaction steps, the properties of the optimal hydrogenation stable catalysts for coal liquefied oil with different boiling ranges are obviously different, and different hydrogenation stable catalysts are necessary to be used for processing coal liquefied raw oil with different boiling ranges in a classified mode, especially for large-scale production of coal liquefied oil.
The aromatic saturation performance, hydrogenation heteroatom removal performance and the requirements of a fluidized bed reaction mode on the strength and density of the catalyst of the hydrogenation stable catalyst for the coal liquefied oil are comprehensively considered, mo and Ni are generally adopted as active components of the hydrogenation stable catalyst for the coal liquefied oil, and the Ni/Mo (atomic ratio) of the active components of the catalyst is generally 0.3-0.4 in order to obtain higher aromatic saturation activity.
Because the hydrogenation stabilizing catalyst of the heavy fraction coal liquefied oil rich in the high-order aromatic hydrocarbon with high metal content is in a boiling back-mixing state and the catalyst is added/discharged on line, the boiling bed catalyst has higher requirements on strength and abrasion so as to reduce the abrasion and breakage of the catalyst. Therefore, the catalyst is required to have a certain high strength and low abrasion, and particularly, the catalyst is required to have a uniform strength distribution, i.e., a strength distribution that is not dispersed, and the number of low-strength particles is required to be as small as possible, so as to avoid the increase in agent consumption caused by breakage of the low-strength particles in a back-mixed state.
For a coal liquefied oil expansion bed hydrogenation stable catalyst, the first chemical property requirement is that the catalyst has good aromatic hydrocarbon hydrogenation saturation capacity, the second chemical property requirement is that the catalyst has good denitrification function on the premise of meeting the first chemical property requirement, and the third chemical property requirement is that the catalyst has good selectivity, namely, less thermal condensation reaction and less thermal cracking reaction, and the catalyst is required to have proper acid strength, acid distribution and the like.
For the hydrogenation stable catalyst of coal liquefied oil expanded bed, the carrier is required to have large pore volume and large specific surface area, and particularly, the carrier is preferably required to have high strength to reduce wear rate, and the techniques described in the following documents can be referred to:
(1) CN100580058C with application date of 2006, 06, 07 discloses a coal liquefied oil boiling bed hydrogenation catalyst carrier and a preparation method thereof. The carrier contains alumina fiber besides the components of the conventional hydrogenation catalyst carrier, and the content of the alumina fiber in the carrier is 3-10 wt%. The carrier has good mechanical strength and wear resistance, improves the stability of the catalyst taking the carrier as the carrier, prolongs the service life of the catalyst and reduces the production cost. Especially, the hydrogenation activity and stability of the catalyst can be improved by adopting the active alumina fiber;
(2) CN101173187B, 11/01/2006, discloses a preparation method of a fluidized bed hydrotreating catalyst, which contains alumina fibers in addition to components of a conventional hydrogenation catalyst, wherein the content of the alumina fibers in the catalyst is 3wt% -10 wt%. The method adopts a complete kneading method, wherein the hydrogenation active metal ions are added into the catalyst in a solution ion mode instead of a granular metal salt mode, so that the metal is more uniformly dispersed, and the mechanical strength of the catalyst is favorably improved. The acidic adhesive in the method is added after the active metal solution wets the mixture of the refractory porous inorganic oxide and the alumina fiber, so that the strong interaction of acid and the refractory porous inorganic oxide and the alumina fiber is greatly slowed down, and the loss of pore volume and specific surface area is reduced;
(3) CN101376829B, whose application date is 27/08/2007, discloses an ebullated bed hydrotreating catalyst and a preparation method thereof, the catalyst adopts an alumina carrier containing alumina fibers and a phosphorus auxiliary agent, wherein part or all of the auxiliary agent phosphorus is introduced in the form of aluminum dihydrogen phosphate. The alumina fiber and the aluminum dihydrogen phosphate are added in the preparation process of the catalyst, so that the mechanical strength and the wear resistance of the catalyst can be improved, the stability of the catalyst is improved, the service life of the catalyst is prolonged, and the production cost is reduced. When the catalyst is used for heavy oil products in fluidized bed hydrogenation treatment, impurities such as nitrogen, sulfur and the like in the oil products can be removed to the maximum extent, the contents of olefin and aromatic hydrocarbon are reduced, and the stability of the product is improved;
(4) for liquefied oil hydrogenation-stable catalysts, part of the relevant information is found in document a01: (1) publication name: direct coal liquefaction process and engineering, pages 240-364; (2) encoding a search graph: ISBN encoding: 9-78703-04308-23; (3) and (3) compiling: wu Xiu Chao, shu Gong Ping, li Ke Jian and Xishun Ming; (4) the publishing company: scientific press.
In the general hydrogenation stabilizing reaction process of the heavy fraction coal liquefied oil, the used carrier of the hydrogenation stabilizing catalyst can be a carrier with a bimodal structure with small holes and middle holes, wherein the diameter of the small holes is 5-10 nanometers, and the diameter of the middle holes is 10-15 nanometers.
In the general hydrogenation stabilizing reaction process of the light fraction coal liquefied oil, the internal pore passage of the carrier of the hydrogenation stabilizing catalyst used can be a carrier with a unimodal structure with a small pore diameter of 7-10 nanometers.
The hydrogenation of coal liquefaction oil stabilizes the catalyst, and along with the extension of the device operation cycle, the catalyst activity gradually reduces, and its reason mainly includes: the carbon generated from the reaction intermediate and the product is deposited on the catalyst, the metal (Ca, mg, fe, na, etc.) in the feedstock oil is deposited on the catalyst, the heteroatom (e.g., nitrogen-containing compound is adsorbed on the catalyst and is a precursor of coking) is adsorbed on the surface of the active metal, the active metal of the catalyst is deteriorated (the sulfidization state of the active metal is considered to be changed due to less sulfur content and more oxygen content in the coal liquefied oil), and the catalyst is mechanically abraded.
The activity of the equilibrium catalyst is very important for the long-period stable operation of the coal liquefied oil hydrogenation stabilizing device, and measures for preventing the activity of the hydrogenation stabilizing catalyst from being reduced comprise the following steps: pretreating the hydrogenation stable raw material to remove components influencing activity, which of course needs to add a reactor; controlling reaction conditions, selecting proper reaction pressure, reaction temperature, airspeed and the like, and preventing the catalyst from being quickly coked to reduce the activity; the physicochemical property of the catalyst is controlled, so that the catalyst has proper specific surface area, pore volume and micropore aperture, and the acidity of the catalyst is also controlled; continuously injecting a sulfur-containing compound into the reaction system to maintain the active metal in a sulfided state; an upflow reactor (such as a fluidized bed reactor) is adopted for periodically replacing the catalyst; regenerating the catalyst, etc.
The activity of the hydrogenation stabilization catalyst is gradually reduced due to carbon deposit, heteroatom compound adsorption, heavy metal deposition, active component state change and the like in the using process, sometimes the catalyst cannot meet the requirement of hydrogenation stabilization depth, the hydrogen supply performance of a circulating solvent is reduced, the conversion rate of coal in a coal liquefaction unit and the yield of liquefied oil are reduced, and meanwhile, the energy consumption and the consumption of a device are increased, so that the old catalyst needs to be regenerated to recover the activity and be reused.
In the coal liquefaction oil hydrogenation stabilization process, for example, a boiling bed hydrogenation reactor is adopted, the activity of the catalyst in the reactor can be kept constant by performing catalyst dosage change on line (periodically discharging a part of the equilibrium catalyst from the reactor, and simultaneously replenishing an equal amount of fresh catalyst or regenerated catalyst), and the discharged equilibrium catalyst needs to be regenerated for being replenished into the reactor for reuse.
Regarding the deactivation of the hydrogenation stabilizing catalyst for coal liquefied oil, the hydrogenation stabilizing catalyst for coal liquefied oil generally uses a vulcanization type catalyst with strong antitoxic ability, and in the hydrogenation stabilizing reaction process, a series of complex reactions such as hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, aromatic hydrocarbon saturation, side chain alkyl removal and the like are carried out, and simultaneously, a hydrodemetallization reaction, a thermal condensation coking reaction and a catalyst active metal metallographical thermal denaturation reaction are carried out.
The reasons for the activity reduction of the coal liquefaction oil hydrogenation stabilization catalyst are complex and generally divided into two main categories: one is temporary deactivation, which allows the catalyst activity to be restored by regeneration or treatment; the other is permanent deactivation, once the catalyst is permanently deactivated, its activity can no longer be restored.
With respect to the temporary deactivation of the catalyst for the hydrogenation stabilization of the coal liquefaction oil, factors causing the temporary deactivation of the catalyst for the hydrogenation stabilization of the coal liquefaction oil include carbon deposition deactivation of the catalyst, adsorption of a basic nitrogen-containing compound on a metal active center, sulfur loss on a metal in a sulfide state, and the like. The existence of an acid center on the hydrogenation stable catalyst can initiate the generation of carbon deposit, the carbon can cover an active center and block a pore channel, the diffusion of raw materials is influenced, and the activity of the catalyst is reduced; the carbon deposit on the catalyst is derived from high-order aromatic hydrocarbon, colloid in the coal liquefied oil, dehydrogenation and thermal condensation products of asphaltene substances carried during production fluctuation, and coke generated by the low-order aromatic hydrocarbon in the reaction process. Because the unsaturated hydrocarbon proportion of the raw material of the coal liquefaction oil hydrogenation stabilizing device is up to more than 70-80 wt%, the coking on the surface of the catalyst is more easily caused. In the hydrogenation stabilization process of the coal liquefaction oil, the influence of the reaction time and the reaction temperature on the carbon deposition amount of the catalyst is the largest. The coal liquefied oil boiling bed hydrogenation stabilizing device adopts a method of periodically replacing a catalyst of a hydrogenation reactor to keep the activity of the catalyst constant, the lower the replacement rate of the catalyst is, the higher the carbon deposit amount on the equilibrium catalyst is, and the carbon deposit amount on the equilibrium catalyst can reach 6 to 10wt percent or even higher. Trace unreacted coal dust carried in the coal liquefied oil can also deposit on the hydrogenation stable catalyst and block the pore channels of the catalyst. The nitrogen content and the alkali nitrogen content in the coal liquefied oil are very high, taking the raw material of Shenhua coal liquefied oil which is stable in hydrogenation as an example, the nitrogen content is 3925ppm, the alkali nitrogen content is about 1500ppm, most of nitrogen-containing compounds in the liquefied oil are alkaline, and heteroatom nitrogen may exist in the forms of carbazole, quinoline, azaphenanthrene, azaanthracene, azapyrene and azafluoranthene; such polar nitrogen-containing compounds are relatively prone to adsorption on acidic active sites causing temporary deactivation of the catalyst.
The main factors of the permanent deactivation of the hydrogenation-stable catalyst for coal liquefied oil include the aggregation of active components of the catalyst at high temperature, the deposition of metal components in the coal liquefied oil, the deposition of Ca, na, fe and other metals in the coal liquefied oil of about 3ppm on the catalyst, and the reduction of the metal sulfide on the catalyst to metal state by hydrogen and difficult re-conversion to sulfide state when the hydrogen sulfide concentration in the gas phase environment of the reaction zone is too low, which results in the permanent deactivation of the hydrogenation-stable catalyst.
The regeneration of a hydrogenation-stabilized catalyst is to remove substances (coke, adsorbates, etc.) causing temporary deactivation of the catalyst by oxidation to restore the activity of the catalyst.
The regeneration of the hydrogenation catalyst is divided into an in-reactor regeneration and an out-of-reactor regeneration. Although in-reactor regeneration can be carried out during the shutdown and maintenance of the hydrogenation device without discharging the catalyst, the in-reactor regeneration of the catalyst also has a series of problems of uneven regeneration, corrosion of equipment and materials of a hydrogenation reaction system caused by regenerated gas and the like, and is rarely used at present.
Off-line regeneration is the most currently used method, and its advantages include: the method has the advantages of no corrosion to equipment and materials of the hydrogenation device, short downtime of the hydrogenation device, accurate control of regeneration conditions, removal of pulverized catalyst, good activity recovery of the catalyst, safety, little pollution and the like.
The hydrogenation stable catalyst can be worn in the using and regenerating processes, and the specific expression is that the diameter of the regenerated catalyst particles is obviously reduced, the particle size is obviously reduced, and a small amount of pulverization loss is generated.
In the direct coal liquefaction process, the solvent mainly plays the following roles: the coal oil slurry is prepared with coal, so that the coal is convenient to convey and pressurize; dissolving coal to prevent the condensation polymerization of free radicals generated by coal pyrolysis; dissolving gas-phase hydrogen to make hydrogen molecule diffuse to coal and catalyst surface; direct hydrogen donation or hydrogen transfer to the radical. Therefore, the requirements of the direct coal liquefaction process on the hydrogen supply solvent are as follows: the density and viscosity are proper, so that the prepared coal oil slurry has proper viscosity; the catalyst has enough 2-4 ring aromatic hydrocarbon content to make the aromatic degree of the hydrogenated product about 0.45, and the solvent can disperse the catalyst and the reaction product in time to prevent free radical polymerization generated by coal pyrolysis.
In the direct coal liquefaction reaction process, the solvent has physical effects of slurrying solid coal powder to improve the conveying performance of materials, improve the thermodynamic properties of the materials, dissolve pyrolysis products of coal and the like, and also has important chemical effects of providing active hydrogen to the pyrolysis products of coal, stabilizing low molecular products of coal pyrolysis or free radicals of the low molecular products of coal pyrolysis and the like. Improve the hydrogen supply performance of the solvent, can ease the reaction conditions and improve the yield of the coal liquefaction oil.
The characteristic parts of the present invention are described below.
The invention relates to a hydrogenation stabilizing method for joint recovery of different distillation range coal liquefied oil zone reaction products, which is characterized by comprising the following steps of:
the direct coal hydrogenation liquefaction process comprises a direct coal hydrogenation liquefaction reaction process and a fractionation process for generating oil through direct coal hydrogenation liquefaction;
in the direct coal hydrogenation liquefaction reaction process, coal dust and coal oil slurry prepared from a hydrogen supply solvent are converted into a direct coal hydrogenation liquefaction reaction product in the presence of hydrogen and a direct coal hydrogenation liquefaction catalyst;
separating the direct coal hydrogenation liquefaction reaction product to obtain direct coal hydrogenation liquefaction generated oil and hydrogen-rich direct coal hydrogenation liquefaction reaction separated gas;
in the fractionation process of the oil generated by the direct liquefaction of the coal hydrogenation, the oil generated by the direct liquefaction of the coal hydrogenation is separated through a separation process comprising a fractionating tower, so that heavy fraction coal liquefied oil rich in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point of 350-520 ℃ is obtained, and light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point lower than 350 ℃ is obtained;
the low-order aromatic hydrocarbon refers to aromatic hydrocarbon with a monocyclic, bicyclic or tricyclic structure;
the high-order aromatic hydrocarbon refers to aromatic hydrocarbon with four or more ring structures;
the average conventional boiling point of the heavy fraction coal liquefied oil is higher than that of the light fraction coal liquefied oil;
the weight concentration of the high-order aromatic hydrocarbons of the heavy fraction coal liquefied oil is higher than that of the high-order aromatic hydrocarbons of the light fraction coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the light fraction coal liquefied oil is less than 30 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the heavy fraction coal liquefied oil is higher than 70 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil and the light fraction coal liquefied oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain reaction products of the first sub-reaction zone, namely first reaction products DV1-P, and reaction products of the second sub-reaction zone, namely second reaction products DV2-P;
the operation mode of the catalyst bed of the first sub-reaction zone DV1 is a limited expansion bed reaction mode with the expansion rate of the catalyst bed not less than 10%;
the operation mode of the DV2 catalyst bed layer of the second sub-reaction zone is a down-flow fixed bed reaction mode or a limited expansion bed reaction mode;
the restricted expanded bed reaction mode refers to the flow of materials upwards and passes through the granular catalyst bed layer to ensure that the granular catalyst bed layer is in an expanded state and the catalyst particles in the expanded bed reaction zone are not discharged out of the reaction zone under the normal operation state;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P and the hydrogen-containing material flow based on the second reaction product DV2-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction area DV1 and/or the second sub-reaction area DV2 for recycling when at least one part of the hydrogen-rich gas exists or does not exist; and/or, after mixing the hydrogen-donor hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor hydrocarbon material flow based on the second reaction product DV2-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry preparation of the raw material coal oil slurry in the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the presence or absence of a separation liquid resulting from the separation of the second reaction product DV2-P is fed into the first sub-reaction zone DV1.
The first coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are respectively arranged in different reactors;
performing gas-liquid separation on the first reaction product DV1-P and the second reaction product DV2-P in different thermal high-pressure separators in the process of separating and recovering the hydrogenation stable reaction products;
the first reaction product DV1-P is separated into heat high-separation oil HHPS1-L and heat high-separation gas HHPS1-V in a heat high-pressure separator HHPS1, and part of the heat high-separation oil HHPS1-L returns to the first sub-reaction zone DV1; introducing part of the hot high-separation oil HHPS1-L into a second sub-reaction zone DV2 in the presence or absence of the hot high-separation oil HHPS 1-L;
the second reaction product DV2-P is separated into hot high-separation oil HHPS2-L and hot high-separation gas HHPS2-V in a hot high-pressure separator HHPS2, and part of the hot high-separation oil HHPS2-L is returned to the second sub-reaction zone DV2 when part of the hot high-separation oil HHPS2-L exists or does not exist; introducing part of the hot high-separation oil HHPS2-L into a first sub-reaction zone DV;
mixing the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS1-V and the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS2-V, carrying out gas-liquid separation to obtain hydrogen-rich gas, and returning at least part of the hydrogen-rich gas to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 for recycling; and/or the presence of a gas in the gas,
and mixing the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS1-L and the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS2-L, and then carrying out a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid.
The second coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are respectively arranged in different reactors;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the first reaction product DV1-P and the second reaction product DV2-P are separated in a thermal high-pressure separator HHPSM31;
the mode of operation is selected from one of the following:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separation element in the hot high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the hot high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 for gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is carried out to obtain a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
part of the mixed separation liquid HHPSM32-L returns to the first sub-reaction zone DV1;
returning the partially mixed separated liquid HHPSM32-L to the second sub-reaction zone DV2 in the presence or absence of the liquid;
and (3) type: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the existence or nonexistence of part of the mixed separation liquid HHPSM33-L to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
and (5) the following steps: and the second reaction product DV2-P enters a reactor provided with the first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
The third coal liquefaction oil hydrogenation stabilization process comprises the following steps:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE1 and both adopt up-flow reaction, the spaces of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are isolated from each other, reaction products DV1-P of the first sub-reaction zone DV1 are discharged from the first sub-reaction zone DV1 to leave the combined reactor MRE1, and reaction products DV2-P of the second sub-reaction zone DV2 are discharged from the second sub-reaction zone DV2 to leave the combined reactor MRE1;
in the process of separating and recovering the hydrogenation stable reaction product, the first reaction product DV1-P and the second reaction product DV2-P are separated in a hot high-pressure separator HHPSM31, and the operation mode is selected from one of the following modes:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separation element in the hot high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the hot high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 to be subjected to gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is divided into a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
returning part of the mixed separation liquid HHPSM32-L to the first sub-reaction zone DV1;
returning the partially mixed separated liquid HHPSM32-L to the second sub-reaction zone DV2 in the presence or absence of the liquid;
and (3) type: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the HHPSM33-L, with or without the presence of a portion of the mixed separated liquid, to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
and (5) the following steps: and the second reaction product DV2-P enters a reactor provided with the first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
The fourth coal liquefaction oil hydrogenation stabilization process comprises the following steps:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE2 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed in the reaction product mixing zone to form a mixed reaction product MRE2-P which leaves the combined reactor MRE2;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the mixed reaction product MRE2-P is separated into heat high-separation oil HHPSM00-L and heat high-separation gas HHPSM00-V in the heat high-pressure separator HHPSM 00;
part of the hot high-molecular oil HHPSM00-L returns to the first sub-reaction zone DV1;
part of the hot high-molecular-weight oil HHPSM00-L is returned to the second sub-reaction zone DV2 in the presence or absence of the hot high-molecular-weight oil HHPSM 00-L.
The fifth hydrogenation stabilization process of the coal liquefaction oil comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE3 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE3-P in the reaction product mixing zone;
a liquid collecting cup is arranged at the top in the combined reactor MRE3, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE3 form a gas-liquid separation chamber for separating a collecting liquid of the separation cup and a net reaction product MRE 3-NP;
returning at least a portion of the separation cup collection to the first sub-reaction zone DV1;
the presence or absence of a part of the separation cup collection is returned to the second sub-reaction zone DV2;
the net reaction product MRE3-NP is discharged from the combined reactor MRE3;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the internal space of each separation cylinder is the second sub-reaction zone DV2, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1.
The sixth hydrogenation stabilization process of the coal liquefaction oil comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE4 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE4-P in the reaction product mixing zone;
the clear gas-liquid separation refers to the separation of a gas-liquid mixture into a gas phase material flow and a liquid phase material flow;
a clear gas-liquid separation type liquid collecting cup is arranged at the top in the combined reactor MRE4, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE4 form a clear gas-liquid separation chamber with a gas-liquid clear separation function;
separating the mixed reaction product MRE4-P into clear collected liquid and a clean reaction product MRE4-NP in a clear gas-liquid separation chamber;
at least part of the clear collection liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a portion of the clear collection liquid is returned to the second sub-reaction zone DV2;
the net reaction product MRE4-NP exits the combined reactor MRE4;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection between the liquid collecting cup and the upper section of the pressure-bearing cylinder section of the combined reactor MRE4 is closed connection, and the space above the bottom plate of the liquid collecting cup is a clear gas-liquid separation zone;
the mixed reaction product MRE4-P below the bottom plate of the liquid collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe positioned in the MRE4 device of the combined reactor passes through the bottom plate of the liquid collecting cup, and a mixed reaction product MRE4-P enters a clear gas-liquid separation area through a liquid guide pipe P61 to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE4-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE4, a liquid guide pipe positioned outside the combined reactor MRE4 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE4 to enter the clear gas-liquid separation zone for gas-liquid separation.
The seventh coal liquefaction oil hydrogenation stabilization process comprises the following steps:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of the combined reactor MRE5 and both adopt upflow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed in the reaction product mixing zone to form a mixed reaction product MRE5-P;
a circulating oil collecting cup and a clean liquid product collecting cup are arranged at the top in the combined reactor MRE5;
the circulating oil collecting cup is a rapid gas-liquid separation functional area with short liquid retention time;
the clean liquid product collecting cup is a slow gas-liquid separation functional area with long liquid retention time;
the fast gas-liquid separation functional area and the slow gas-liquid separation functional area are separated by a separation area partition plate K30, and liquid in the fast gas-liquid separation functional area and liquid in the slow gas-liquid separation functional area are allowed to flow back and forth across the upper edge of the separation area partition plate K30;
part of the mixed reaction product MRE5-P is separated into fast gas and fast liquid in a fast gas-liquid separation functional area;
part of the mixed reaction product MRE5-P is separated into slow gas and slow liquid in a slow gas-liquid separation functional zone;
at least part of the fast-separating liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a part of the fast-separating liquid is returned to the second sub-reaction zone DV2;
at least part of the slowly separating liquid is discharged out of the combined reactor MRE5 as a clean liquid product;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection among the circulating oil liquid collecting cup, the clean liquid product liquid collecting cup and the upper section of the pressure-bearing cylinder section of the combined reactor MRE5 is closed connection, and the space above the bottom plate of the liquid collecting cup is a gas-liquid separation zone; the gas-liquid separation area is divided into a fast gas-liquid separation functional area and a slow gas-liquid separation functional area;
the mixed reaction product MRE5-P below the bottom plate of the circulating oil collecting cup and the clean liquid product collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe P71 positioned in the MRE5 device of the combined reactor passes through a bottom plate of the circulating oil liquid collecting cup and the bottom plate of the clean liquid product liquid collecting cup, and a mixed reaction product MRE5-P enters a gas-liquid separation area through the liquid guide pipe to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE5-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE5, a liquid guide pipe positioned outside the combined reactor MRE5 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE5 to enter the clear gas-liquid separation zone for gas-liquid separation.
The combined hydrogenation stabilization method of the 3 kinds of coal liquefaction oil comprises the following steps:
the method comprises the steps of separating the direct coal hydrogenation liquefaction product oil through a separation process comprising a fractionating tower in the fractionation process of the direct coal hydrogenation liquefaction product oil to obtain heavy fraction coal liquefaction oil rich in high-order aromatic hydrocarbons and mainly composed of hydrocarbons with the conventional boiling point higher than 400 ℃, middle fraction coal liquefaction oil mainly composed of hydrocarbons with the conventional boiling point of 300-400 ℃ and light fraction coal liquefaction oil mainly composed of hydrocarbons with the conventional boiling point lower than 300 ℃;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil, the light fraction coal liquefied oil and the medium fraction coal liquefied oil respectively enter a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain a first reaction product DV1-P of the first sub-reaction zone DV1, a second reaction product DV2-P of the second sub-reaction zone DV2 and a third reaction product DV3-P of the third sub-reaction zone; the operation mode of the DV1 catalyst bed layer of the first sub-reaction zone is an ebullated bed reaction mode;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P, the hydrogen-containing material flow based on the second reaction product DV2-P and the hydrogen-containing material flow based on the third reaction product DV3-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 and/or the third sub-reaction zone DV3 for recycling; and/or, after mixing the hydrogen-donor hydrocarbon stream based on the first reaction product DV1-P, the hydrogen-donor hydrocarbon stream based on the second reaction product DV2-P and the hydrogen-donor hydrocarbon stream based on the third reaction product DV3-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry blending of the coal-oil slurry of the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
the presence or absence of a separation liquid obtained by separating the first reaction product DV1-P enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a first sub-reaction zone DV1;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the third reaction product DV3-P to the third sub-reaction zone DV3 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the third reaction product DV3-P with or without the existence enters a first sub-reaction zone DV1;
the presence or absence of a separation liquid obtained by separating the third reaction product DV3-P is fed into the second sub-reaction zone DV2.
The combined hydrogenation stabilization method of the 3 kinds of coal liquefaction oil can be as follows:
the method comprises the following steps that a coal liquefaction oil hydrogenation stabilization reaction process is adopted, and a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE6 and are subjected to upflow reaction.
The operation method of the invention can be as follows:
the method comprises the steps of separating coal hydrogenation direct liquefaction generated oil through a separation process comprising a fractionating tower in a fractionation process of coal hydrogenation direct liquefaction generated oil to obtain heavy fraction coal liquefaction oil and light fraction coal liquefaction oil;
the fractionating process of the coal hydrogenation direct liquefaction produced oil comprises an atmospheric fractionating tower system and a vacuum fractionating tower system which are operated in series, and distillate oil discharged from a nearest distillation outlet above a feeding hole of the highest boiling point hydrocarbon feeding material of the atmospheric fractionating tower enters a first sub-reaction zone DV1 to be jointly treated with the heavy fraction coal liquefaction oil.
The operation method of the invention can be as follows:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, heavy fraction coal liquefaction oil and light fraction coal liquefaction oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, wherein the different operation conditions refer to different one or more of the types of hydrogenation stabilization catalysts, liquid residence time, operation temperature, bed expansion ratio, circulation ratio of circulation oil in the sub-reaction zones and operation pressure, and the method has one or more of the following characteristics:
(1) the pore channel distribution of the hydrogenation stable catalyst carrier of the first sub-reaction zone DV1 has a double-peak characteristic, the peak value of a first pore channel is between 5 and 10 nanometers, and the peak value of a second pore channel is between 10 and 15 nanometers;
(2) the hydrogenation stable catalyst of the first sub-reaction zone DV1 is a mixture of 2 hydrogenation stable catalysts, the pore channel distribution peak value of the carrier of one hydrogenation stable catalyst is between 5 and 10 nanometers, and the pore channel distribution peak value of the carrier of the other hydrogenation stable catalyst is between 10 and 20 nanometers;
(3) the active metal oxide content of the hydrogenation stabilizing catalyst of the first sub-reaction zone DV1 is at least 115% of the active metal oxide content of the hydrogenation stabilizing catalyst of the second sub-reaction zone DV2;
(4) the liquid hourly space velocity of the hydrogenation stable catalyst in the first sub-reaction zone DV1 is not more than 80% of the liquid hourly space velocity of the hydrogenation stable catalyst in the second sub-reaction zone DV2;
(5) the average reaction temperature of the hydrogenation stabilizing catalyst in the first sub-reaction zone DV1 is at least 5 ℃ higher than that of the hydrogenation stabilizing catalyst in the second sub-reaction zone DV2.
The operation method of the invention can be as follows:
the organic metal removal rate of the reaction process of the first time that the heavy fraction coal liquefied oil flows through the first sub-reaction zone DV1 is selected from one of the following: (1) higher than 50%; (2) higher than 70%; (3) higher than 85%.
The operation method of the invention can be as follows:
the expansion rate of a catalyst bed layer of a first sub-reaction zone DV1 for treating the heavy fraction coal liquefied oil is selected from 1 of the following types:
(1) a bubbling bed with an expansion rate of 25-55%;
(2) expanded beds with expansion ratios between 10 and 25%.
The operation method of the invention can be as follows:
the operation mode of the hydrogenation stabilizing catalyst bed layer of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil in the coal liquefied oil hydrogenation stabilizing reaction process is selected from 1 of the following modes:
(1) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 25 to 55 percent of that of a fluidized bed;
(2) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 10-25 percent of that of the expanded bed;
(3) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 0.1-10 percent;
(4) the process medium is operated in a down-flow mode, and the catalyst bed layer is a fixed bed.
The hydrogenation-stabilizing operating conditions of the present invention are typically:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 280-415 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.5-2.0 h -1 The chemical hydrogen consumption of fresh raw material per unit weight is 0.6-2.5 wt%;
the operating conditions of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 250-405 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.8-2.5 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.5 to 1.7% by weight.
The hydrogenation stabilizing operation conditions of the invention are generally as follows:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 320-400 ℃, and the gas-liquid volume ratio is 200-1000 Nm 3 T, the space velocity of the catalyst volume is 0.9-1.8 h -1 The chemical hydrogen consumption of fresh raw material per unit weight is 0.9-1.7 wt%;
the operating conditions of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 370-390 ℃, and the gas-liquid volume ratio is 200 ℃1000Nm 3 T, the space velocity of the catalyst volume is 1.0-2.0 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.8-1.5 wt%.
In general, the average aromatic carbon rate of conventional liquid hydrocarbons having a conventional boiling point higher than 200 ℃ in the entire hydrogenation-stabilized reaction product is 0.35 to 0.42.
In general, the average hydrogen donor index of conventional liquid hydrocarbons having a conventional boiling point above 200 ℃ in the total hydrogenation-stabilized reaction product of the present invention is from 23 to 28.
According to the invention, generally, fresh coal liquefaction oil and circulating oil flow through the first sub-reaction zone DV1, and the weight flow of the circulating oil flowing through the first sub-reaction zone DV1 is 1-5 times of the weight flow of the fresh coal liquefaction oil flowing through the first sub-reaction zone DV1;
fresh coal liquefaction oil and circulating oil flow through the second sub-reaction zone DV2, and the weight flow of the circulating oil flowing through the second sub-reaction zone DV2 is 1-3 times of the weight flow of the fresh coal liquefaction oil flowing through the second sub-reaction zone DV2.
According to the invention, in the coal liquefaction oil hydrogenation stabilization reaction process, the first sub-reaction zone DV1 and the second sub-reaction zone DV2 can be arranged on a lower catalyst support disk and/or a bed layer feeding distribution disk in a pressure-bearing shell of the combined reactor and both adopt up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel, and generally, the horizontal cross-sectional area of the first sub-reaction zone DV1 accounts for 30-60% of the horizontal cross-sectional area of the combined hydrogenation reactor.
In the invention, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor and both adopt up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel;
usually, the separation element between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is a cylindrical or regular polygonal cylinder.
The nature of the hydrogenation-stabilising catalyst of the invention may be:
second sub-reaction zone DV1The carrier of the hydrogenation stable catalyst and the carrier of the hydrogenation stable catalyst used in the second sub-reaction zone DV2 are both a mixture of alumina and silica, and SiO is taken as the reference based on the weight of the carrier 2 The content of the impurity is limited to Na in the range of 2.3 to 2.6 wt% 2 O content of not more than 0.05 wt%, fe 2 O 3 The content is less than or equal to 0.03 weight percent, the gibbsite content is less than or equal to 3.0 weight percent, the pore volume is 0.9 to 1.35ml/g, and the specific surface is 300 to 370m 2 /g；
The hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 has the following active metal oxide content by taking the weight of the catalyst as a reference: WO 3 9.9-15.3 wt% of MoO 3 7.4 to 11.4 weight percent of NiO, 2.3 to 3.6 weight percent of NiO, and B 2 O 3 The content of (B) is 2.1-3.1 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g；
The hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 has the following active metal oxide content by taking the weight of the catalyst as a reference: WO 3 7.0 to 10.5 weight percent of MoO 3 5.2 to 8.0 weight percent of NiO, 1.6 to 2.5 weight percent of NiO, B 2 O 3 The content of (B) is 1.4-2.2 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g。
The nature of the hydrogenation-stabilising catalyst of the invention may be:
the carrier of the hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 is a mixture of alumina and silica, and the pore distribution characteristics of the carrier are as follows: the proportion of the surface area of the nanometer pore canal lower than 5 to the total pore surface area is 5-10 percent, the proportion of the surface area of the nanometer pore canal between 5 and 10 to the total pore surface area is 30-40 percent, the peak value is between 6.5 and 7.5 nanometers, the proportion of the surface area of the nanometer pore canal between 10 and 15 to the total pore surface area is 30-40 percent, the peak value is between 11.5 and 13.5 nanometers, and the proportion of the surface area of the nanometer pore canal higher than 15 to the total pore surface area is 10-20 percent;
the carrier of the hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 is a mixture of alumina and silica, and the distribution characteristics of the pore channels are as follows: the ratio of the surface area of the nanometer pore canal lower than 5 to the total pore surface area is 10-20%, the ratio of the surface area of the nanometer pore canal 5-10 to the total pore surface area is 70-80%, the peak value is between 6.5-7.5 nanometers, and the ratio of the surface area of the nanometer pore canal higher than 10 to the total pore surface area is 10-20%.
The operation method of the invention can be as follows:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, the expansion rate of a hydrogenation stabilization catalyst bed layer of a first sub-reaction zone DV1 is 25-55%, and the expansion rate of a hydrogenation stabilization catalyst bed layer of a second sub-reaction zone DV2 for treating light fraction coal liquefaction oil is 25-55%.
The operation method of the invention can be as follows:
the preparation solvent of the oil-coal slurry is composed of a short-range circulating solvent RDV and a hydrogen supply solvent with a hydrogen supply index larger than 25.5 from a hydrogenation stable reaction product separation and recovery process; the flow rate of the short-range circulating solvent RDV is 3-20% of the total oil-coal slurry preparation solvent; the average hydrogen supply index of all the oil coal slurry preparation solvents is more than 23;
in the fractionation process of the coal hydrogenation direct liquefaction produced oil, the coal hydrogenation direct liquefaction produced oil is separated through a separation process comprising a fractionating tower, so that a first heavy fraction coal liquefied oil mainly composed of hydrocarbon components with the conventional boiling points of 350-490 ℃ is obtained, a second heavy fraction coal liquefied oil containing at least 70 wt% of 5-ring aromatic hydrocarbons in the whole coal liquefied oil and having the average conventional boiling point higher than that of the first heavy fraction coal liquefied oil is obtained, and a light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling points lower than 350 ℃ is obtained;
at least part of the second heavy fraction coal liquefaction oil is used as a short-path circulating solvent RDV for preparing the coal oil slurry without undergoing a coal liquefaction oil hydrogenation stabilization reaction process;
in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-donor-containing hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor-containing hydrocarbon material flow based on the second reaction product DV2-P are mixed and then are subjected to a separation process comprising a fractionating tower to obtain hydrogen-donor-rich hydrocarbon liquid, at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen supply solvent for blending the raw material oil coal slurry in the coal hydrogenation direct liquefaction reaction process, and the hydrogen supply index of the hydrogen supply solvent is more than 25.5.
The operation method of the invention can be as follows:
the method comprises the steps that in the direct coal hydrogenation liquefaction reaction process, the content of inert components in coal powder for preparing the oil-coal-slurry is lower than 10%, and the RDV flow rate of an oil-coal-slurry short-distance circulating solvent is 5-15% of the total oil-coal-slurry preparation solvent.
The operation method of the invention can be as follows:
and in the coal liquefaction oil hydrogenation stabilization reaction process, all new hydrogen enters the reaction zone of the first sub-reaction zone DV1.
The general control principle of the gas phase hydrogen sulfide concentration in the hydrogenation reaction process of the present invention is described in detail.
Any make-up sulfur may be added to any of the hydrogenation processes as needed, but is typically added to the uppermost hydrogenation process inlet to ensure that the minimum hydrogen sulfide concentration required for the reaction process, such as a desired value of 500ppm (v) or 1000ppm (v) or 3000ppm (v), is not below the minimum specified value to ensure the required hydrogen sulfide partial pressure for the catalyst to ensure the required sulfidation profile for the catalyst. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or liquid sulfur or carbon disulfide or dimethyl disulfide which generates hydrogen sulfide after being contacted with high-temperature hydrogen gas.
The general principles of the high pressure separation process of the hydrogenation reaction effluent of the present invention are described in detail below.
The high-pressure separation process of the hydrogenation reaction effluent usually comprises a cold high-pressure separator, when the hydrocarbon oil in the hydrogenation reaction effluent has high density (for example, the density is close to the water density) or high viscosity or is emulsified with water and difficult to separate, or contains solid particles or fully utilizes the heat of hot oil, a hot high-pressure separator with the operation temperature usually being 150-450 ℃ is also needed, the hydrogenation reaction effluent enters the hot high-pressure separator to be separated into hot high-molecular gas mainly consisting of hydrogen in volume and hot high-molecular oil liquid mainly consisting of conventional liquid hydrocarbon and possibly existing solids, the hot high-molecular gas enters the cold high-pressure separator with the operation temperature usually being 20-80 ℃ to be separated into cold high-molecular oil and cold high-molecular gas, and the following aims are achieved due to the fact that a large amount of high-boiling-point components enter the hot high-molecular oil liquid: the cold high-fraction oil becomes less dense or less viscous or easily separated from water. The high-pressure separation process of the hydrogenation reaction effluent is provided with the hot high-pressure separator, and the high-pressure separation process also has the advantage of reducing heat loss because the hot high-pressure separation oil liquid can avoid the cooling process of using an air cooler or a water cooler for hot high-pressure separation gas. Meanwhile, part of the hot high-oil liquid can be returned to the upstream hydrogenation reaction process for recycling, so as to improve the overall raw material property of the hydrogenation reaction process receiving the circulating oil, or the circulating hot high-oil can be subjected to circulating hydrogenation.
Between the hot high pressure separation part and the cold high pressure separation part, a temperature high pressure separation part can be arranged according to the requirement, at the moment, the hot high pressure separation gas is cooled to form a gas-liquid two-phase material, the gas is separated into a temperature high pressure separation gas mainly comprising hydrogen in volume and a temperature high pressure separation oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solid in a temperature high pressure separator, and the temperature high pressure separation gas enters the cold high pressure separation part for cooling and gas-liquid separation.
Before the hydrogenation effluent or hot high-pressure gas or warm high-pressure gas enters the cold high-pressure separation section, the temperature is usually lowered (generally by heat exchange with the feed of the reaction section) to about 220 to 100 ℃ (the temperature should be higher than the crystallization temperature of ammonia hydrosulfide and the crystallization temperature of ammonia chloride in the gas phase of the hydrogenation effluent), and then washing water is usually injected into the reaction effluent to form the hydrogenation effluent after water injection, 2 or more water injection points may be needed, the washing water is used for absorbing ammonia and other impurities such as hydrogen chloride and the like, and the aqueous solution after ammonia absorption necessarily absorbs hydrogen sulfide. In the cold high-pressure separation part, the effluent of the hydrogenation reaction after water injection is separated into: a cold high-molecular gas mainly composed of hydrogen in volume, a cold high-molecular oil mainly composed of conventional liquid hydrocarbon and dissolved hydrogen, and a cold high-molecular water mainly composed of water and dissolved with ammonia and hydrogen sulfide. The cold high-moisture water generally has an ammonia content of 0.5 to 15% (w), preferably 1 to 8% (w). One purpose of the washing water injection is to absorb ammonia and hydrogen sulfide in the hydrogenation reaction effluent, prevent the formation of ammonia hydrosulfide or ammonia polysulfide crystals from blocking the heat exchanger channels, and increase the pressure drop of the system. The injection amount of the washing water is determined according to the following principle: on the one hand, the washing water is divided into vapor phase water and liquid phase water after being injected into the hydrogenation reaction effluent, and the liquid phase water amount is required to be more than zero, and is preferably 30 percent or more of the total amount of the washing water; in a further aspect, the wash water is used to absorb ammonia from the hydrogenation effluent, to prevent the high partial gas from having too high an ammonia concentration, and to reduce the activity of the catalyst, and generally the lower the ammonia volume concentration of the high partial gas, the better, the lower the ammonia volume concentration of the high partial gas, the more generally not greater than 200ppm (v), and the better the ammonia volume concentration of the high partial gas is not greater than 50ppm (v). The operation pressure of the cold high-pressure separator is the difference between the hydrogenation reaction part pressure and the actual pressure drop, and the difference between the operation pressure of the cold high-pressure separator and the hydrogenation reaction pressure is not too low or too high, generally 0.35-3.2 MPa, and generally 0.5-1.5 MPa. The hydrogen volume concentration value of the cold high-molecular gas should not be too low (leading to a rise in the operating pressure of the plant), and should generally be not less than 70% (v), preferably not less than 80% (v), and most preferably not less than 85% (v). At least one part of the cold high-molecular gas, which is usually 85-100 percent, is returned to the hydrogenation reaction part for recycling, so as to provide the hydrogen amount and the hydrogen concentration which are necessary for the hydrogenation reaction part; in order to increase the investment efficiency of the plant, it is necessary to ensure that the recycle hydrogen concentration does not fall below the aforementioned lower limit, for which reason, depending on the specific feedstock properties, reaction conditions, product distribution, a portion of the cold high-molecular gas may be removed to remove methane and ethane produced by the reaction. For discharged cold high-molecular gas, conventional membrane separation process or pressure swing adsorption process or oil washing process can be adopted to realize the separation of hydrogen and non-hydrogen gas components, and the recovered hydrogen is used as new hydrogen.
For the direct coal hydrogenation liquefaction reaction process RU, because of the conventional gases hydrocarbon, CO 2 The yield is huge, and most of cold high-fraction gas is about 70-100% of cold high-fraction gas, permeable hydrogen obtained after purification by a membrane separation process is pressurized and then returns to the hydrogenation reaction process, and non-permeable gas is pressurized and returns to the hydrogenation reaction process for recycling after PSA hydrogen extraction or 'steam conversion hydrogen production + PSA hydrogen extraction'.
Fresh hydrogen is fed into the hydrogenation section to replenish hydrogen consumed in the hydrogenation process, and the higher the concentration of fresh hydrogen, the better, the more preferred the concentration of fresh hydrogen is, the less 95% (v) and the better the more preferred the concentration of fresh hydrogen is, the less 99% (v) or more. All of the fresh hydrogen may be introduced into any of the hydrogenation reaction sections.
In any reaction process, the used hydrogen material flow can be all new hydrogen, can be all recycle hydrogen, and can be the mixed gas of the new hydrogen and the recycle hydrogen.
Claims (28)
1. The hydrogenation stabilizing method for jointly recovering the coal liquefied oil zone reaction products with different distillation ranges is characterized by comprising the following steps of:
the direct coal hydrogenation liquefaction process comprises a direct coal hydrogenation liquefaction reaction process and a fractionation process for generating oil through direct coal hydrogenation liquefaction;
in the direct coal hydrogenation liquefaction reaction process, coal dust and coal oil slurry prepared from a hydrogen supply solvent are converted into a direct coal hydrogenation liquefaction reaction product in the presence of hydrogen and a direct coal hydrogenation liquefaction catalyst;
separating the direct coal hydrogenation liquefaction reaction product to obtain direct coal hydrogenation liquefaction generated oil and hydrogen-rich direct coal hydrogenation liquefaction reaction separated gas;
in the fractionation process of the oil generated by the direct liquefaction of the coal hydrogenation, the oil generated by the direct liquefaction of the coal hydrogenation is separated through a separation process comprising a fractionating tower, so that heavy fraction coal liquefied oil rich in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point of 350-520 ℃ is obtained, and light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling point lower than 350 ℃ is obtained;
the low-order aromatic hydrocarbon refers to aromatic hydrocarbon with a monocyclic, bicyclic or tricyclic structure;
the high-order aromatic hydrocarbon refers to aromatic hydrocarbon with four or more ring structures;
the average conventional boiling point of the heavy fraction coal liquefied oil is higher than that of the light fraction coal liquefied oil;
the weight concentration of the high-order aromatic hydrocarbons of the heavy fraction coal liquefied oil is higher than that of the high-order aromatic hydrocarbons of the light fraction coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the light fraction coal liquefied oil is less than 30 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
the weight of the high-order aromatic hydrocarbons in the heavy fraction coal liquefied oil is higher than 70 percent of the total weight of the high-order aromatic hydrocarbons in the whole coal liquefied oil;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil and the light fraction coal liquefied oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain reaction products of the first sub-reaction zone, namely first reaction products DV1-P, and reaction products of the second sub-reaction zone, namely second reaction products DV2-P;
the operation mode of the catalyst bed of the first sub-reaction zone DV1 is a limited expansion bed reaction mode with the expansion rate of the catalyst bed not less than 10%;
the operation mode of the DV2 catalyst bed layer of the second sub-reaction zone is a down-flow fixed bed reaction mode or a limited expansion bed reaction mode;
the limited expansion bed reaction mode refers to that material flow passes through the granular catalyst bed layer in an up-flow mode to enable the granular catalyst bed layer to be in an expansion state, and catalyst particles in the expansion bed reaction zone are not discharged out of the reaction zone under a normal operation state;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P and the hydrogen-containing material flow based on the second reaction product DV2-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction area DV1 and/or the second sub-reaction area DV2 for recycling when at least one part of the hydrogen-rich gas exists or does not exist; and/or, after mixing the hydrogen-donor hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor hydrocarbon material flow based on the second reaction product DV2-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry preparation of the raw material coal oil slurry in the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the presence or absence of a separation liquid resulting from the separation of the second reaction product DV2-P is passed to the first sub-reaction zone DV1.
2. The hydrogenation stabilization method according to claim 1, characterized in that:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are respectively arranged in different reactors;
performing gas-liquid separation on the first reaction product DV1-P and the second reaction product DV2-P in different thermal high-pressure separators in the process of separating and recovering the hydrogenation stable reaction products;
the first reaction product DV1-P is separated into heat high-separation oil HHPS1-L and heat high-separation gas HHPS1-V in a heat high-pressure separator HHPS1, and part of the heat high-separation oil HHPS1-L returns to the first sub-reaction zone DV1; introducing part of the hot high-separation oil HHPS1-L into a second sub-reaction zone DV2 in the presence or absence of the hot high-separation oil HHPS 1-L;
the second reaction product DV2-P is separated into hot high-separation oil HHPS2-L and hot high-separation gas HHPS2-V in a hot high-pressure separator HHPS2, and part of the hot high-separation oil HHPS2-L is returned to the second sub-reaction zone DV2 when part of the hot high-separation oil HHPS2-L exists or does not exist; introducing part of the hot high-separation oil HHPS2-L into a first sub-reaction zone DV;
mixing the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS1-V and the hydrogen-containing material flow based on the hot high-pressure gas distribution HHPS2-V, carrying out gas-liquid separation to obtain hydrogen-rich gas, and returning at least part of the hydrogen-rich gas to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 for recycling; and/or the presence of a gas in the gas,
and mixing the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS1-L and the hydrogen-donor hydrocarbon stream based on the thermal high-separation liquid HHPS2-L, and then carrying out a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid.
3. The hydrogenation stabilization method according to claim 1, characterized in that:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are respectively arranged in different reactors;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the first reaction product DV1-P and the second reaction product DV2-P are separated in a thermal high-pressure separator HHPSM31;
the mode of operation is selected from one of the following:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separating element in the thermal high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the thermal high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 for gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is carried out to obtain a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
returning part of the mixed separation liquid HHPSM32-L to the first sub-reaction zone DV1;
returning the part of the mixed separation liquid HHPSM32-L with or without existence back to the second sub-reaction zone DV2;
and (3) type: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the HHPSM33-L, with or without the presence of a portion of the mixed separated liquid, to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
and (5) the following steps: and the second reaction product DV2-P enters a reactor provided with the first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
4. The hydrogenation stabilization method according to claim 1, characterized in that:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE1 and both adopt up-flow reaction, the spaces of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are isolated from each other, reaction products DV1-P of the first sub-reaction zone DV1 are discharged from the first sub-reaction zone DV1 to leave the combined reactor MRE1, and reaction products DV2-P of the second sub-reaction zone DV2 are discharged from the second sub-reaction zone DV2 to leave the combined reactor MRE1;
in the process of separating and recovering the hydrogenation stable reaction product, the first reaction product DV1-P and the second reaction product DV2-P are separated in a hot high-pressure separator HHPSM31, and the operation mode is selected from one of the following modes:
the 1 st: the first reaction product DV1-P and the second reaction product DV2-P respectively enter different gas-liquid separation zones separated by a separation element in the hot high-pressure separator HHPSM31 for gas-liquid separation, the upper gas phase spaces of the different gas-liquid separation zones are communicated, the lower liquid phase spaces of the different gas-liquid separation zones are not communicated, and the separated gas of the first reaction product DV1-P and the separated gas of the second reaction product DV2-P are mixed and then leave the hot high-pressure separator HHPSM31 as mixed separated gas;
the separated liquid DV1-PL of the first reaction product DV1-P leaves the hot high-pressure separator HHPSM31;
the separated liquid DV2-PL of the second reaction product DV2-P leaves the hot high-pressure separator HHPSM31;
after mixing the hydrogen-donating hydrocarbon stream of the separation liquid DV1-PL based on the first reaction product DV1-P with the hydrogen-donating hydrocarbon stream of the separation liquid DV2-P based on the second reaction product DV, performing a separation process comprising a fractionating tower to obtain a hydrogen-donating hydrocarbon-rich liquid;
the 2 nd: the first reaction product DV1-P and the second reaction product DV2-P respectively enter the same gas-liquid separation zone in the hot high-pressure separator HHPSM32 to be subjected to gas-liquid separation, separation gas mixing and separation liquid mixing, and the separation is divided into a mixed separation gas HHPSM32-V and a mixed separation liquid HHPSM32-L;
part of the mixed separation liquid HHPSM32-L returns to the first sub-reaction zone DV1;
returning the partially mixed separated liquid HHPSM32-L to the second sub-reaction zone DV2 in the presence or absence of the liquid;
and (3) a step of: mixing the first reaction product DV1-P and the second reaction product DV2-P, and then introducing the mixture into a hot high-pressure separator HHPSM33 for gas-liquid separation to obtain a mixed separated gas HHPSM33-V and a mixed separated liquid HHPSM33-L;
part of the mixed separation liquid HHPSM33-L returns to the first sub-reaction zone DV1;
returning the HHPSM33-L, with or without the presence of a portion of the mixed separated liquid, to the second sub-reaction zone DV2;
and 4, the method comprises the following steps: the first reaction product DV1-P enters a reactor provided with a second sub-reaction zone DV2 and is mixed with an intermediate reaction product or a final reaction product of the light fraction coal liquefied oil;
and (5) the following steps: and the second reaction product DV2-P enters a reactor provided with a first sub-reaction zone DV1 and is mixed with an intermediate reaction product or a final reaction product of the heavy fraction coal liquefied oil.
5. The hydrogenation stabilization method according to claim 1, characterized in that:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE2 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed in the reaction product mixing zone to form a mixed reaction product MRE2-P which leaves the combined reactor MRE2;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the internal space of each separation cylinder is the second sub-reaction zone DV2, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the separation and recovery process of the hydrogenation stable reaction product is carried out, and the mixed reaction product MRE2-P is separated into heat high-separation oil HHPSM00-L and heat high-separation gas HHPSM00-V in the heat high-pressure separator HHPSM 00;
part of the hot high-molecular oil HHPSM00-L returns to the first sub-reaction zone DV1;
the existence or nonexistence of part of the hot high-separation oil HHPSM00-L returns to the second sub-reaction zone DV2.
6. The hydrogenation stabilization method according to claim 1, characterized in that:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE3 and both adopt upflow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed in the reaction product mixing zone to form a mixed reaction product MRE3-P;
a liquid collecting cup is arranged at the top in the combined reactor MRE3, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE3 form a gas-liquid separation chamber for separating a collecting liquid of the separation cup and a net reaction product MRE 3-NP;
at least part of the separation cup collection is returned to the first sub-reaction zone DV1;
the presence or absence of a part of the separation cup collection is returned to the second sub-reaction zone DV2;
the net reaction product MRE3-NP is discharged from the combined reactor MRE3;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of the separating cylinders is the second sub-reaction zone DV2, and the space between the separating cylinders and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1.
7. The hydrogenation stabilization method according to claim 1, characterized in that:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE4 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE4-P in the reaction product mixing zone;
the clear gas-liquid separation refers to the separation of a gas-liquid mixture into a gas phase material flow and a liquid phase material flow;
a clear gas-liquid separation type liquid collecting cup is arranged at the top in the combined reactor MRE4, and the liquid collecting cup and an upper end enclosure of the combined reactor MRE4 form a clear gas-liquid separation chamber with a gas-liquid clear separation function;
separating the mixed reaction product MRE4-P into clear collected liquid and a clean reaction product MRE4-NP in a clear gas-liquid separation chamber;
at least part of the clear collected liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a portion of the clear collection liquid is returned to the second sub-reaction zone DV2;
the net reaction product MRE4-NP exits the combined reactor MRE4;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection between the liquid collecting cup and the upper section of the pressure-bearing cylinder section of the combined reactor MRE4 is closed connection, and the space above the bottom plate of the liquid collecting cup is a clear gas-liquid separation zone;
the mixed reaction product MRE4-P below the bottom plate of the liquid collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe positioned in the MRE4 device of the combined reactor passes through the bottom plate of the liquid collecting cup, and a mixed reaction product MRE4-P enters a clear gas-liquid separation area through a liquid guide pipe P61 to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE4-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE4, a liquid guide pipe positioned outside the combined reactor MRE4 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE4 to enter the clear gas-liquid separation zone for gas-liquid separation.
8. The hydrogenation stabilization method according to claim 1, characterized in that:
secondly, in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE5 and both adopt up-flow reaction, the space above the first sub-reaction zone DV1 and the space above the second sub-reaction zone DV2 are communicated with each other to form a reaction product mixing zone, and a first reaction product DV1-P and a second reaction product DV2-P are mixed into a mixed reaction product MRE5-P in the reaction product mixing zone;
a circulating oil collecting cup and a clean liquid product collecting cup are arranged at the top in the combined reactor MRE5;
the circulating oil collecting cup is a rapid gas-liquid separation functional area with short liquid retention time;
the clean liquid product collecting cup is a slow gas-liquid separation functional area with long liquid retention time;
the fast gas-liquid separation functional area and the slow gas-liquid separation functional area are separated by a separation area partition plate K30, and liquid in the fast gas-liquid separation functional area and liquid in the slow gas-liquid separation functional area are allowed to flow back and forth across the upper edge of the separation area partition plate K30;
part of the mixed reaction product MRE5-P is separated into fast gas and fast liquid in a fast gas-liquid separation functional area;
part of the mixed reaction product MRE5-P is separated into slow gas and slow liquid in a slow gas-liquid separation functional zone;
at least part of the fast-separating liquid is returned to the first sub-reaction zone DV1;
the presence or absence of a part of the fast-separating liquid is returned to the second sub-reaction zone DV2;
at least part of the slowly separating liquid is discharged out of the combined reactor MRE5 as a clean liquid product;
the spatial relationship between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is selected from one of the following:
the 1 st: the separation elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separation cylinders, the inner space of each separation cylinder is the first sub-reaction zone DV1, and the space between each separation cylinder and the pressure-bearing shell of the reactor is the second sub-reaction zone DV2;
the 2 nd: the separating elements of the first sub-reaction zone DV1 and the second sub-reaction zone DV2 are separating cylinders, the inner space of each separating cylinder is the second sub-reaction zone DV2, and the space between each separating cylinder and the pressure-bearing shell of the reactor is the first sub-reaction zone DV1;
the connection among the circulating oil liquid collecting cup, the liquid collecting cup for the purified liquid product and the upper section of the pressure-bearing cylinder section of the combined reactor MRE5 is closed connection, and a space above the bottom plate of the liquid collecting cup is a gas-liquid separation zone; the gas-liquid separation area is divided into a fast gas-liquid separation functional area and a slow gas-liquid separation functional area;
the mixed reaction product MRE5-P below the bottom plate of the circulating oil collecting cup and the clean liquid product collecting cup enters the gas-liquid separation zone in an operation mode selected from one of the following modes:
the 1 st: a liquid guide pipe P71 positioned in the combined reactor MRE5 penetrates through the bottom plates of the circulating oil liquid collecting cup and the clean liquid product liquid collecting cup, and a mixed reaction product MRE5-P enters a gas-liquid separation area through the liquid guide pipe to be subjected to gas-liquid separation;
the 2 nd: the mixed reaction product MRE5-P sequentially flows through a mixed reaction product discharge port on the wall of the combined reactor MRE5, a liquid guide pipe positioned outside the combined reactor MRE5 and a feeding port of a clear gas-liquid separation zone positioned on the wall of the combined reactor MRE5 to enter the clear gas-liquid separation zone for gas-liquid separation.
9. The hydrogenation stabilization method according to claim 1, characterized in that:
the method comprises the steps of separating the direct coal hydrogenation liquefaction product oil through a separation process comprising a fractionating tower in the fractionation process of the direct coal hydrogenation liquefaction product oil to obtain heavy fraction coal liquefaction oil rich in high-order aromatic hydrocarbons and mainly composed of hydrocarbons with the conventional boiling point higher than 400 ℃, middle fraction coal liquefaction oil mainly composed of hydrocarbons with the conventional boiling point of 300-400 ℃ and light fraction coal liquefaction oil mainly composed of hydrocarbons with the conventional boiling point lower than 300 ℃;
secondly, in the coal liquefied oil hydrogenation stabilization reaction process, the heavy fraction coal liquefied oil, the light fraction coal liquefied oil and the medium fraction coal liquefied oil respectively enter a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 with different operation conditions, and hydrogenation stabilization reactions with different aromatic hydrocarbon saturation depths are carried out to respectively obtain a first reaction product DV1-P of the first sub-reaction zone DV1, a second reaction product DV2-P of the second sub-reaction zone DV2 and a third reaction product DV3-P of the third sub-reaction zone; the operation mode of the DV1 catalyst bed layer of the first sub-reaction zone is an ebullated bed reaction mode;
thirdly, in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-rich gas and/or the hydrogen-rich hydrocarbon liquid are/is recovered in a combined manner;
mixing the hydrogen-containing material flow based on the first reaction product DV1-P, the hydrogen-containing material flow based on the second reaction product DV2-P and the hydrogen-containing material flow based on the third reaction product DV3-P, and then carrying out gas-liquid separation to obtain hydrogen-rich gas, wherein at least one part of the hydrogen-rich gas is returned to the first sub-reaction zone DV1 and/or the second sub-reaction zone DV2 and/or the third sub-reaction zone DV3 for recycling; and/or, after mixing the hydrogen-donor hydrocarbon stream based on the first reaction product DV1-P, the hydrogen-donor hydrocarbon stream based on the second reaction product DV2-P and the hydrogen-donor hydrocarbon stream based on the third reaction product DV3-P, performing a separation process comprising a fractionating tower to obtain a hydrogen-donor-rich hydrocarbon liquid, wherein at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen-supplying solvent for the slurry blending of the coal-oil slurry of the coal hydrogenation direct liquefaction reaction process;
separating the first reaction product DV1-P to obtain a separation liquid, and returning the separation liquid to the first sub-reaction zone DV1;
the separated liquid obtained by separating the first reaction product DV1-P with or without the existence enters a second sub-reaction zone DV2;
the presence or absence of a separation liquid obtained by separating the first reaction product DV1-P enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the second reaction product DV2-P to the second sub-reaction zone DV2 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a first sub-reaction zone DV1;
the separated liquid obtained by separating the second reaction product DV2-P with or without the existence enters a third sub-reaction zone DV3;
returning the separation liquid obtained by separating the third reaction product DV3-P to the third sub-reaction zone DV3 in the presence or absence of the separation liquid;
the separated liquid obtained by separating the third reaction product DV3-P with or without the existence enters a first sub-reaction zone DV1;
the presence or absence of a separation liquid obtained by separating the third reaction product DV3-P is fed into the second sub-reaction zone DV2.
10. The hydrogenation stabilization method according to claim 9, characterized in that:
the method comprises the following steps that a coal liquefaction oil hydrogenation stabilization reaction process is adopted, and a first sub-reaction zone DV1, a second sub-reaction zone DV2 and a third sub-reaction zone DV3 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor MRE6 and are subjected to upflow reaction.
11. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the method comprises the steps of separating coal hydrogenation direct liquefaction generated oil through a separation process comprising a fractionating tower in a fractionation process of coal hydrogenation direct liquefaction generated oil to obtain heavy fraction coal liquefaction oil and light fraction coal liquefaction oil;
the fractionating process of the coal hydrogenation direct liquefaction produced oil comprises an atmospheric fractionating tower system and a vacuum fractionating tower system which are operated in series, and distillate oil discharged from a nearest distillation outlet above a feeding hole of the highest boiling point hydrocarbon feeding material of the atmospheric fractionating tower enters a first sub-reaction zone DV1 to be jointly treated with the heavy fraction coal liquefaction oil.
12. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, heavy fraction coal liquefaction oil and light fraction coal liquefaction oil respectively enter a first sub-reaction zone DV1 and a second sub-reaction zone DV2 which have different operation conditions, wherein the different operation conditions refer to different one or more of the types of hydrogenation stabilization catalysts, liquid residence time, operation temperature, bed expansion ratio, circulation ratio of circulation oil in the sub-reaction zones and operation pressure, and the method has one or more of the following characteristics:
(1) the pore channel distribution of the hydrogenation stable catalyst carrier of the first sub-reaction zone DV1 has a double-peak characteristic, the peak value of a first pore channel is between 5 and 10 nanometers, and the peak value of a second pore channel is between 10 and 15 nanometers;
(2) the hydrogenation stable catalyst of the first sub-reaction zone DV1 is a mixture of 2 hydrogenation stable catalysts, the pore channel distribution peak value of the carrier of one hydrogenation stable catalyst is between 5 and 10 nanometers, and the pore channel distribution peak value of the carrier of the other hydrogenation stable catalyst is between 10 and 20 nanometers;
(3) the active metal oxide content of the hydrogenation stabilizing catalyst of the first sub-reaction zone DV1 is at least 115% of the active metal oxide content of the hydrogenation stabilizing catalyst of the second sub-reaction zone DV2;
(4) the liquid hourly space velocity of the hydrogenation stable catalyst in the first sub-reaction zone DV1 is not more than 80% of the liquid hourly space velocity of the hydrogenation stable catalyst in the second sub-reaction zone DV2;
(5) the average reaction temperature of the hydrogenation stabilizing catalyst in the first sub-reaction zone DV1 is at least 5 ℃ higher than that of the hydrogenation stabilizing catalyst in the second sub-reaction zone DV2.
13. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the organic metal removal rate of the reaction process of the first time that the heavy fraction coal liquefied oil flows through the first sub-reaction zone DV1 is selected from one of the following: (1) higher than 50%; (2) higher than 70%; (3) higher than 85%.
14. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the expansion rate of a catalyst bed layer of a first sub-reaction zone DV1 for treating the heavy fraction coal liquefied oil is selected from 1 of the following types:
(1) a bubbling bed with an expansion rate of 25-55%;
(2) expanded beds with expansion ratios between 10 and 25%.
15. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the operation mode of the hydrogenation stabilizing catalyst bed layer of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil in the coal liquefied oil hydrogenation stabilizing reaction process is selected from 1 of the following modes:
(1) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 25 to 55 percent of that of a fluidized bed;
(2) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 10-25 percent of that of the expanded bed;
(3) the process medium is operated in an up-flow mode, and the expansion rate of a catalyst bed layer is 0.1-10 percent;
(4) the process medium is operated in a down-flow mode, and the catalyst bed layer is a fixed bed.
16. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 280-415 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.5-2.0 h -1 The chemical hydrogen consumption of fresh raw material per unit weight is 0.6-2.5 wt%;
the operating conditions of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil are as follows:
the pressure of the reactor is 8-17 MPa, the reaction temperature is 250-405 ℃, and the gas-liquid volume ratio is 50-4500 Nm 3 T, the space velocity of the catalyst volume is 0.8-2.5 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.5 to 1.7% by weight.
17. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the operation conditions of the first sub-reaction zone DV1 for treating the heavy fraction coal liquefaction oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 320-400 ℃, and the gas-liquid volume ratio is 200-1000 Nm 3 T, catalystThe volume space velocity is 0.9 to 1.8h -1 Chemical hydrogen consumption per unit weight of fresh raw material is 0.9-1.7 wt%;
the operating conditions of the second sub-reaction zone DV2 for treating the light fraction coal liquefied oil are as follows:
the pressure of the reactor is 10-15 MPa, the reaction temperature is 370-390 ℃, and the gas-liquid volume ratio is 200-1000 Nm 3 T, the space velocity of the catalyst volume is 1.0-2.0 h -1 The chemical hydrogen consumption per unit weight of fresh raw material is 0.8-1.5 wt%.
18. The hydrogenation stabilization process according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, characterized in that:
the average aromatic carbon rate of the conventional liquid hydrocarbon with the conventional boiling point higher than 200 ℃ in the total hydrogenation stable reaction product is 0.35-0.42.
19. The hydrogenation stabilization process according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, characterized in that:
the average hydrogen-donating index of the conventional liquid hydrocarbon with the conventional boiling point higher than 200 ℃ in the total hydrogenation stable reaction product is 23-28.
20. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
fresh coal liquefaction oil and circulating oil flow through the first sub-reaction zone DV1, wherein the weight flow of the circulating oil flowing through the first sub-reaction zone DV1 is 1-5 times that of the fresh coal liquefaction oil flowing through the first sub-reaction zone DV1;
fresh coal liquefied oil and circulating oil flow through the second sub-reaction zone DV2, and the weight flow of the circulating oil flowing through the second sub-reaction zone DV2 is 1-3 times that of the fresh coal liquefied oil flowing through the second sub-reaction zone DV2.
21. The process of claim 4 or 5 or 6 or 7 or 8, wherein:
the coal liquefaction oil hydrogenation stabilization reaction process comprises the steps that a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst supporting disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor and both adopt up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel, and the horizontal cross-sectional area of the first sub-reaction zone DV1 accounts for 30-60% of the horizontal cross-sectional area of the combined hydrogenation reactor.
22. The process of claim 4 or 5 or 6 or 7 or 8, wherein:
the method comprises the following steps that in the coal liquefaction oil hydrogenation stabilization reaction process, a first sub-reaction zone DV1 and a second sub-reaction zone DV2 are arranged on a lower catalyst support disc and/or a bed layer feeding distribution disc in a pressure-bearing shell of a combined reactor and are subjected to up-flow reaction to form the first sub-reaction zone DV1 and the second sub-reaction zone DV2 which are connected in parallel;
the separation element between the first sub-reaction zone DV1 and the second sub-reaction zone DV2 is a cylindrical or regular polygonal cylinder.
23. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the carrier of the hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 and the carrier of the hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 are both a mixture of alumina and silica, and based on the weight of the carriers, siO 2 The content of the impurity is limited to Na in the range of 2.3 to 2.6 wt% 2 O content of not more than 0.05 wt%, fe 2 O 3 The content is less than or equal to 0.03 weight percent, the content of gibbsite is less than or equal to 3.0 weight percent, the pore volume is 0.9 to 1.35ml/g, and the specific surface area is 300 to 370m 2 /g；
The hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 has the following active metal oxide content by taking the weight of the catalyst as a reference: WO 3 9.9-15.3 wt% of MoO 3 7.4 to 11.4 weight percent of NiO, 2.3 to 3.6 weight percent of NiO, and B 2 O 3 The content of (B) is 2.1-3.1 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g；
The hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 has the following active metal oxide content by taking the weight of the catalyst as a reference: WO 3 7.0 to 10.5 weight percent of MoO 3 5.2 to 8.0 weight percent of NiO, 1.6 to 2.5 weight percent of NiO, B 2 O 3 The content of (B) is 1.4-2.2 wt%, the pore volume is 0.9-1.35 ml/g, and the specific surface area is 300-370 m 2 /g。
24. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the carrier of the hydrogenation stabilizing catalyst used in the first sub-reaction zone DV1 is a mixture of alumina and silica, and the pore distribution characteristics of the carrier are as follows: the ratio of the surface area of the nanometer pore channels lower than 5 to the total pore surface area is 5-10 percent, the ratio of the surface area of the nanometer pore channels between 5 and 10 to the total pore surface area is 30-40 percent, the peak value is positioned between 6.5 and 7.5 nanometers, the ratio of the surface area of the nanometer pore channels between 10 and 15 to the total pore surface area is 30-40 percent, the peak value is positioned between 11.5 and 13.5 nanometers, and the ratio of the surface area of the nanometer pore channels higher than 15 to the total pore surface area is 10-20 percent;
the carrier of the hydrogenation stabilizing catalyst used in the second sub-reaction zone DV2 is a mixture of alumina and silica, and the distribution characteristics of the pore channels are as follows: the ratio of the surface area of the nanometer pore canal lower than 5 to the total pore surface area is 10-20%, the ratio of the surface area of the nanometer pore canal 5-10 to the total pore surface area is 70-80%, the peak value is between 6.5-7.5 nanometers, and the ratio of the surface area of the nanometer pore canal higher than 10 to the total pore surface area is 10-20%.
25. The hydrogenation stabilization process according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, characterized in that:
and the second reaction process of hydrogenation stabilization of the coal liquefaction oil is implemented, wherein the bed expansion rate of the hydrogenation stabilization catalyst of the first sub-reaction zone DV1 is 25-55%, and the bed expansion rate of the hydrogenation stabilization catalyst of the second sub-reaction zone DV2 for treating the light fraction coal liquefaction oil is 25-55%.
26. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8, wherein:
the preparation solvent of the oil-coal slurry is composed of a short-range circulating solvent RDV and a hydrogen supply solvent with a hydrogen supply index larger than 25.5 from a hydrogenation stable reaction product separation and recovery process; the flow rate of the short-range circulating solvent RDV is 3-20% of the total oil-coal slurry preparation solvent; the average hydrogen supply index of all the oil coal slurry preparation solvents is more than 23;
in the fractionation process of the coal hydrogenation direct liquefaction produced oil, the coal hydrogenation direct liquefaction produced oil is separated through a separation process comprising a fractionating tower, so that a first heavy fraction coal liquefied oil mainly composed of hydrocarbon components with the conventional boiling points of 350-490 ℃ is obtained, a second heavy fraction coal liquefied oil containing at least 70 wt% of 5-ring aromatic hydrocarbons in the whole coal liquefied oil and having the average conventional boiling point higher than that of the first heavy fraction coal liquefied oil is obtained, and a light fraction coal liquefied oil lean in high-order aromatic hydrocarbons and mainly composed of hydrocarbon components with the conventional boiling points lower than 350 ℃ is obtained;
at least part of the second heavy fraction coal liquefaction oil is used as a short-path circulating solvent RDV for preparing the coal oil slurry without undergoing a coal liquefaction oil hydrogenation stabilization reaction process;
in the process of separating and recovering the hydrogenation stable reaction product, the hydrogen-donor-containing hydrocarbon material flow based on the first reaction product DV1-P and the hydrogen-donor-containing hydrocarbon material flow based on the second reaction product DV2-P are mixed and then are subjected to a separation process comprising a fractionating tower to obtain hydrogen-donor-rich hydrocarbon liquid, at least one part of the hydrogen-donor-rich hydrocarbon liquid is used as a hydrogen supply solvent for blending the raw material oil coal slurry in the coal hydrogenation direct liquefaction reaction process, and the hydrogen supply index of the hydrogen supply solvent is more than 25.5.
27. The hydrogenation stabilization process of claim 26, wherein:
the method comprises the steps that in the direct coal hydrogenation liquefaction reaction process, the content of inert components in coal powder for preparing the oil-coal-slurry is lower than 10%, and the RDV flow rate of an oil-coal-slurry short-distance circulating solvent is 5-15% of the total oil-coal-slurry preparation solvent.
28. The hydrogenation stabilization method according to claim 1, characterized in that:
and in the coal liquefaction oil hydrogenation stabilization reaction process, all new hydrogen enters the reaction zone of the first sub-reaction zone DV1.
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| CN102559256A (en) * | 2011-10-16 | 2012-07-11 | 何巨堂 | Combination method of hydrogenised aromatic hydrocarbon partial saturation of coal-liquefied oil |
| CN109554186A (en) * | 2017-09-27 | 2019-04-02 | 何巨堂 | The tandem compound method of direct hydrogenation liquefaction of coal section and heavy hydrocarbon heat from hydrogenation cracking zone |
| CN110066687A (en) * | 2019-04-16 | 2019-07-30 | 洛阳瑞华新能源技术发展有限公司 | Liquid product recycle hydrogenates the hydrocarbon material expanded bed method of hydrotreating of Jia Fufang material among grade |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559256A (en) * | 2011-10-16 | 2012-07-11 | 何巨堂 | Combination method of hydrogenised aromatic hydrocarbon partial saturation of coal-liquefied oil |
| CN109554186A (en) * | 2017-09-27 | 2019-04-02 | 何巨堂 | The tandem compound method of direct hydrogenation liquefaction of coal section and heavy hydrocarbon heat from hydrogenation cracking zone |
| CN110066687A (en) * | 2019-04-16 | 2019-07-30 | 洛阳瑞华新能源技术发展有限公司 | Liquid product recycle hydrogenates the hydrocarbon material expanded bed method of hydrotreating of Jia Fufang material among grade |
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