CN109722265B - Coal hydrogenation direct liquefaction process using reactors with internal parallel reaction zones - Google Patents
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Abstract
The direct coal hydrogenation liquefaction reaction process of the reactor with the internal parallel reaction zones is suitable for the reaction processes of 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 series reactor 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.
Description
Technical Field
The invention relates to a coal hydrogenation direct liquefaction reaction process using a reactor with internal parallel reaction zones, which is suitable for the reaction processes of coal hydrogenation direct 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 series reactor 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.
Background
For the direct coal hydrogenation liquefaction reaction process, when multiple paths of coal slurry with the same coal concentration or multiple paths of coal slurry with different coal concentrations or coal slurry and heavy oil are processed, different feeds are processed in parallel in different reaction spaces, namely different raw materials are processed in parallel, and a subsequent combined reaction process is arranged.
The idea of the invention is: the direct coal hydrogenation liquefaction reaction process of the reactor with the internal parallel reaction zones is suitable for the reaction processes of 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 to reduce the number of reactors, and can realize the combination of a plurality of small reactor circulating pumps to reduce the number of circulating pumps, thereby saving investment; RE can effectively utilize the total height of the series reactor 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.
Certainly, the distilled oil of the oil generated in the coal hydrogenation direct liquefaction reaction process RU (intermediate or final reaction process) can be introduced into the coal hydrogenation direct liquefaction reaction process RU for secondary recycling, can be used as solvent oil for blending coal slurry, and can be subjected to cyclic thermal cracking. For example, diesel oil (distillate oil with a conventional boiling point of 260-330 ℃) and/or wax oil (distillate oil with a conventional boiling point of 330-530 ℃) in the produced oil in the coal hydrogenation direct liquefaction reaction process AU can be returned to the RU for cyclic cracking, so that naphtha can be produced in a large amount.
Of course, the distilled oil of the oil generated in the coal hydrogenation direct liquefaction reaction process AU (intermediate or final reaction process) can be introduced into the hydrogenation stabilization reaction process MR to produce the hydrogen supply solvent, and then the coal hydrogenation direct liquefaction reaction process AU is introduced for recycling.
When the invention is used in the process of co-refining kerosene, non-coal derived oil can be used for preparing coal slurry so as to enter the initial step synchronous reaction of the coal hydrogenation direct liquefaction reaction process AU, and the coal slurry can also be added into the intermediate reaction step of the coal hydrogenation direct liquefaction reaction process AU to carry out the latter half combined reaction.
The core of the invention is the combination of reaction zones, forming a reactor of combined structure.
The technical scheme similar to the invention is not reported.
The invention aims to provide a direct coal hydrogenation liquefaction reaction process using a reactor with internal parallel reaction zones, which is suitable for a direct coal hydrogenation liquefaction reaction process or a kerosene co-refining process.
Disclosure of Invention
The invention relates to a coal hydrogenation direct liquefaction reaction process using a reactor with internal parallel reaction zones, which is characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and possibly catalyst, coal slurry containing coal dust is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least 1 reaction section, including at least one reaction section using a reactor with internal parallel reaction zones;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation uses the upflow reactor KRE with the internal parallel reaction zone, at least 2 parallel reaction zones KARE and reaction zones KBRE are separated in the reaction space of the reactor KRE, a liquid collecting cup and a collected liquid guiding-out system are arranged in the liquid separating space at the top of the reactor KRE, and the working mode is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
a material based on the mixture MP-TO-TS, used as top wet space feedstock 100F;
in a liquid separation space formed by a reactor top shell and a liquid collecting cup at the top of the reactor KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products;
and fifthly, in a liquid material circulating system, at least one part of collecting liquid KRE-RL is pressurized by a circulating pump and then returns to the reaction space of the reactor KRE for circulating processing.
The invention generally sets up a mixed reaction zone KCRE, which is characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and possibly catalyst, coal slurry containing coal dust is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least 1 reaction section, including at least one reaction section of a reactor with an internal parallel reaction zone;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation has upflow reactor KRE of inside parallel reaction zone, cuts out 2 at least parallel reaction zone KARE and reaction zone KBRE in reactor KRE's reaction space, divides the liquid space and sets up liquid collecting cup and collection liquid derivation system in reactor KRE's top, and its working method is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
performing at least one part of coal hydrogenation direct liquefaction reaction on the mixture MP-TO-TS-based material TO convert the mixture MP-TO-TS into a mixed reaction zone product KCRE-P;
at least a portion of the mixed reaction zone product KCRE-P is used as top liquid space feed 100F;
and fourthly, in a liquid separation space formed by the top shell of the reactor and the liquid collecting cup at the top of the KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products.
In the present invention, generally, in a liquid circulation system of the reactor KRE having the reaction zones connected in parallel therein, at least a part of the collected liquid KRE-RL is pressurized by the circulation pump and then returned to the reaction zone KARE of the reactor KRE or/and the reaction zone KBRE for circulation processing.
In the invention, generally, the reactor KRE with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the upstream reaction material refers to reaction material flowing upwards in the main body direction in the KRE reactor.
In the present invention, generally, in a reactor KRE having internal parallel reaction zones, respective ascending reaction material distributors are provided in the parallel reaction zones, and an ascending reaction material distributor is provided in the mixed reaction zone KCRE.
In the invention, generally, inside a KRE (KRE) internally connected with a reaction zone in parallel, respective ascending reaction material distributors are arranged in the reaction zone in parallel, and an ascending reaction material distributor is arranged in a KCRE (KCRE) mixing reaction zone, thereby forming material distributors arranged in series;
a material input pipe containing a liquid raw material introduction space DH is arranged in a space DH between the lower section distributor and the upper section distributor and at a position close to the upper section distributor;
the upward reaction material refers to a reaction material flowing upwards in the main body direction in the KRE reactor;
the cross-section distributor refers to a material distributor which is horizontally arranged in the reactor KRE and can evenly distribute the ascending material from the lower space of the reactor KRE to the upper reaction space of the distributor.
According to the invention, in the direct coal hydrogenation liquefaction reaction process RU, slurry containing materials based on KRE products of reactors in parallel connection with reaction zones inside enter the downstream direct coal hydrogenation liquefaction reaction process to carry out deep coal liquefaction reaction;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by the direct liquefaction reaction of coal hydrogenation.
According to the invention, in the direct coal hydrogenation liquefaction reaction process RU, slurry-containing slurry feeding of a reactor KRE in an internal parallel reaction area is slurry-containing material based on the product of an upstream direct coal hydrogenation liquefaction reactor;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by the direct liquefaction reaction of coal hydrogenation.
In the present invention, usually, the liquid circulation system of the reactor KRE is connected in parallel with the inside of the reactor KRE, and at least a part of the collected liquid KRE-RL is pressurized by the circulating pump and then returned to the reaction zone KARE of the reactor KRE or/and the reaction zone KBRE for circulation processing.
In the invention, generally, a liquid material circulating system of the reactor KRE in a reaction zone is connected in parallel inside, at least one part of collected liquid KRE-RL is pressurized by the same 1 circulating pump and then divided into at least 2 circulating materials, and each circulating material enters different reaction zones of the reactor KRE for circulating processing.
In the present invention, the operation mode of the KRE reactor with parallel reaction zones inside can be selected from 1 or more of the following:
firstly, a suspension bed reactor;
② a fluidized bed reactor;
and thirdly, a suspended bed and a fluidized bed reactor, wherein a fluidized bed reaction zone is arranged in the reaction space of the suspended bed.
According to the invention, the liquid material entering the reactor KRE of the internal parallel reaction zone can be selected from 1 or more of the following liquid materials:
oil coal slurry or coal liquefaction intermediate product slurry is subjected to coal hydrogenation direct liquefaction reaction in the coal hydrogenation direct liquefaction reaction process;
secondly, under the condition that one path of liquid material is ensured to be oil coal slurry or coal liquefaction intermediate product slurry, the other path of liquid material is distilled oil which is directly liquefied and reacted to generate oil based on coal hydrogenation, and hydrogenation thermal cracking reaction is carried out in a KRE reactor;
thirdly, under the condition that one path of liquid material is oil coal slurry or coal liquefaction intermediate product liquid material, performing hydrogenation stabilization reaction based on distilled oil which is generated by coal hydrogenation direct liquefaction reaction in a hydrogenation stabilization reaction process MR to produce hydrogen supply solvent oil required by the coal hydrogenation direct liquefaction reaction process, wherein the hydrogen supply solvent oil enters a reactor KRE to participate in coal liquefaction reaction;
fourthly, under the condition that one path of liquid material is ensured to be the coal oil slurry or the coal liquefaction intermediate product slurry, the other path of liquid material is non-coal-based heavy oil, and the coal oil is formed.
According to the invention, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering the reaction zone KARE contains oil coal slurry or coal liquefaction intermediate product slurry;
in the reactor KRE internally connected in parallel with the reaction zone, the material KF2 entering the reaction zone KBRE contains coal oil slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil.
According to the invention, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering a KARE reaction zone contains oil coal slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil;
in the reactor KRE with the internal parallel reaction zones, the material KF2 entering the reaction zone KBRE contains oil coal slurry or coal liquefaction intermediate product slurry.
The invention discloses a coal hydrogenation direct liquefaction reaction process RU, which comprises at least 2 reaction sections of slurry material serial operation, wherein the first reaction section is a reaction section formed by reactors with internal parallel reaction zones, and the flow mode of the coal hydrogenation direct liquefaction reaction process RU can be selected from 1 or more of the following steps:
the method comprises the following steps that firstly, a coal hydrogenation direct liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid phase from the first reaction section;
a second reaction section is set, and an up-flow type expanded bed coal hydrogenation direct liquefaction reactor 2RE is used; the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is used as lower feed to enter the lower part of the reactor 2RE and flow upwards to pass through the main reaction area, and is converted into a reaction product 2RTP to be discharged out of the reactor 2 RE;
the direct coal hydrogenation liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid material 1ALPA mainly comprising solid-liquid-containing materials in weight from the first reaction section;
setting up a second reaction section, using an up-flow expanded bed coal hydrogenation direct liquefaction reactor 2RE, enabling a product liquid material 1ALPA of the first reaction section to enter the lower part of the reactor 2RE as a lower feed to flow upwards to pass through a main reaction area, converting into a reaction product 2RTP and discharging out of the reactor 2 RE;
meanwhile, the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is taken as an upper feed to enter the upper part of the reactor 2RE and is mixed and contacted with the materials in the reactor 2 RE;
the reactor 2RE is provided with a top liquid collecting cup, and the collected liquid is circularly returned to the lower reaction space of the reactor 2RE for circular processing;
the direct coal hydrogenation liquefaction reaction process RU comprises a pre-hydrogenation reaction section OPRE and a first reaction section which are operated in series;
in the pre-hydrogenation reaction section OPRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction pre-hydrogenation reaction and is converted into a coal hydrogenation direct liquefaction pre-hydrogenation reaction product OPRE-RP, and at least one part of the pre-hydrogenation reaction product OPRE-RP enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction;
the coal hydrogenation direct liquefaction reaction process RU comprises a pre-hydrogenation reaction section OPRE and a first reaction section which are operated in series;
in the pre-hydrogenation reaction section OPRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction pre-hydrogenation reaction and is converted into coal hydrogenation direct liquefaction pre-hydrogenation reaction product OPRE-RP, liquid material OPLPX mainly comprising solid slurry in weight is obtained based on the pre-hydrogenation reaction product OPRE-RP, and at least a part of the liquid material product OPLPX enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction.
According to the invention, in the general process of direct coal hydrogenation liquefaction reaction RU, the conversion rate of the anhydrous and ashless components of the raw material coal is 70-98%.
According to the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the coal slurry raw material is processed, and simultaneously, the non-coal-based heavy oil is processed, wherein the conversion rate of the hydrogenation thermal cracking reaction of the non-coal-based heavy oil is 40-90%.
In the invention, in general, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering the reaction zone KARE is thick coal slurry;
in the KRE, a material KF2 entering a reaction zone KBRE is dilute coal slurry, and the absolute difference of the coal concentration of the dilute coal slurry KF2 lower than that of the dense coal slurry KF1 is 5-35%.
According to the invention, usually, dilute coal slurry and thick coal slurry are simultaneously processed in a reactor KRE of an internal parallel reaction zone, wherein the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%.
According to the invention, usually, dilute coal slurry and thick coal slurry are processed simultaneously in a reactor KRE with an internal parallel reaction zone, wherein the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%; the ratio of the weight flow WF2-W of the thick coal slurry WF2 to the weight flow WF1-W of the thin coal slurry WF1 is a slurry ratio K100, K100 is WF2-W/WF1-W, and K100 is 0.01-1.0.
The invention, in general, in the direct coal liquefaction reaction of coal hydrogenationIn the process RU, the operation conditions of the coal hydrogenation direct liquefaction reaction process of the coal powder are as follows: the reaction temperature is 400-490 ℃, the reactor pressure is 6-30 MPa, the volume concentration of gas-phase hydrogen is 50-95%, and the gas-liquid ratio is 300-2500 Nm3The addition amount of the direct coal hydrogenation liquefaction catalyst is 0.1-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is that the molar ratio of sulfur in the cocatalyst to the active metal of the catalyst is 1.0-2.0, the solid concentration of the coal slurry is 40-60 mass%, and the reaction retention time is 0.5-4 hours.
In the invention, in the process of the direct coal hydrogenation liquefaction reaction RU, the used direct coal hydrogenation liquefaction catalyst can be a composite hydrogenation catalyst which comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the direct coal hydrogenation liquefaction catalyst is less than 2 wt%; the direct coal hydrogenation liquefaction catalyst is powdery particles with the particle diameter of 1-100 mu m.
According to the invention, in the coal hydrogenation direct liquefaction reaction process RU, the coal hydrogenation direct liquefaction catalyst used can be a nanometer ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
In the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the hydrogen-donating solvent oil contained in the coal slurry feed mainly comprises hydrocarbons with the conventional boiling point of 250-530 ℃.
In the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the ratio of the weight of the hydrogen donor solvent DS to the weight of the coal powder is 0.5-2.0 calculated by all the fed materials.
In the invention, generally, in a direct coal hydrogenation liquefaction reaction process RU, at least one path of raw materials in all liquid hydrocarbon-containing raw materials contains a hydrogen donor, wherein the hydrogen donor mainly comprises hydrocarbons with conventional boiling points of 250-530 ℃, the weight content of part of saturated aromatic hydrocarbons in the hydrogen donor is more than 15%, and the aromatic carbon rate is 0.35-0.70.
In the invention, in the process of direct coal hydrogenation liquefaction reaction RU, at least one part of slurry blending solvent oil contained in the raw material coal slurry can be selected from 1 or more of the following materials:
firstly, middle-low temperature coal tar or distillate oil thereof or oil products obtained in the thermal processing process of the coal tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
② high temperature coal tar or distillate oil thereof or oil product material flow obtained in the thermal processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
③ fractionating oil of the product of the direct coal hydrogenation liquefaction process or oil products obtained in the thermal processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
shale oil or distillate oil thereof or oil products obtained in the thermal processing process of the shale oil or distillate oil; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
ethylene cracking tar or oil products obtained in the thermal processing process of the ethylene cracking tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
oil products obtained in the oil-based heavy oil-heating processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
seventhly, petroleum sand-based heavy oil or oil products obtained in the thermal processing process of the petroleum sand-based heavy oil; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
other hydrocarbon oils with a content of aromatics higher than 40% by weight.
Drawings
The present invention will be described in detail below with reference to the accompanying drawings, which are drawn for the purpose of describing the invention, but are not intended to limit the scope of the application of the invention.
Fig. 1 is a schematic diagram of 2 parallel suspension bed hydrogenation reactors for a typical coal hydrogenation direct liquefaction process, wherein 1ARE belongs to an upflow suspension bed hydrogenation reactor system provided with a forced liquid product circulation system, and 1BRE belongs to a bubbling bed type suspension bed hydrogenation reactor system, and can be used for simultaneously and respectively processing 2 different raw materials, such as coal slurry in one way and non-coal-based heavy oil in one way. The process has the operation targets that in the process of co-refining kerosene, the thermal cracking time of the kerosene is shorter than the coal liquefaction reaction time, the hydrogen supply function of the relatively excessive hydrogen supply agent component in the slurry at the rear part of the direct coal hydrogenation liquefaction reaction system is fully utilized, and the synchronous superposition of the coal material pyrolysis free radical concentration peak stage in the initial reaction process of direct coal hydrogenation liquefaction and the heavy oil pyrolysis free radical concentration peak stage in the initial reaction process of heavy oil hydrogenation pyrolysis is avoided, so that the expansion and the contention of the oil material pyrolysis free radical and the coal material pyrolysis free radical for the active hydrogen provided by the hydrogen supply agent are inevitably caused, and the normal liquefaction reaction in the initial reaction process of direct coal hydrogenation liquefaction is inhibited; during operation, one raw material is coal slurry, and the other raw material is heavy oil.
The flow schematic diagram of the conventional technical scheme shown in fig. 1 is a parallel coupling reaction system composed of 2 typical suspended bed hydrogenation reactors for the direct coal hydrogenation liquefaction process, wherein products of a reactor 1ARE and a reactor 1BRE ARE mixed in the reactor 1ARE (at the top), a liquid collecting cup 1AV at the top of the reactor 1ARE shared, and the circulation of liquid phase products of 2 reactors can be completed by using 1 circulating pump; and the internal structure of the reactor 1BRE in FIG. 1 is simpler than that of the reactor 1ARE in FIG. 1, and a liquid collecting cup and a liquid guide pipe ARE omitted; the circulating liquid material in the 2 reactors is a mixture of the liquid-phase product from 1ARE and the liquid-phase product from 1BRE, so that the 2 reactors form a coupled coal hydrogenation direct liquefaction reaction system.
As shown in FIG. 1, in the reactor 1ARE system, the mixture 1AF of coal slurry and hydrogen fed through line 151 is mixed with the circulating liquid phase 1ARL1 (which may contain a gaseous phase and contains liquid phase products from 1ARE and 1 BRE) fed through line 159 to form a mixed material 1ATF, which is fed through line 152 into the bottom of the reactor 1ARE and is usually predistributed by a feed distributor 1ATFS (not shown) installed above the feed inlet at the bottom of the reactor to distribute the feed AS evenly AS possible over the entire horizontal feed cross-section of the distribution tray 1 AS; the gas, liquid and solid particle mixed phase material from the lower part of the distribution disc 1AS flows upwards after passing through the distribution disc 1AS, and is subjected to direct coal hydrogenation liquefaction reaction in the ascending process of the main reaction space of the reactor 1ARE to be converted into a top product 1ARP of the reactor 1 ARE.
As shown in FIG. 1, the overhead product 1ARP, after passing through the annular gap between the inner wall of the upper part of the reactor 1ARE and the outer wall of the liquid collecting cup 1AV, enters the partial liquid removing space consisting of the reactor overhead wall and the liquid collecting cup 1AV in the upper part of the reactor 1ARE, and is different from the conventional flow scheme shown in FIG. 1 in that the partial liquid removing is carried out after mixing with the product 1BRTP from the reactor 1 BRE. As shown in FIG. 1, the liquid in the top mixed product preferentially settles into the collection cup 1AV under the action of gravity, bubbles ARE gradually removed in the descending process of the interior of the collection cup 1AV, the bubble-removed circulating liquid phase 1ARL enters the conduit 1AVP at the bottom of the collection cup 1AV and flows downwards to be discharged out of the reactor 1ARE, enters the circulating pressure pump 1APUMP through the conduit 158, and the pressurized first circulating liquid phase 1ARL1 is conveyed through the conduit 159, then is mixed with the mixture 1AF1 to form a mixture 1ATF, and is conveyed into the reactor 1ARE through the conduit 152 for circulating processing.
As shown in FIG. 1, the top product 1ARP is separated into a circulating liquid phase 1ARL and a net product 1ARTP, the net product 1ARTP is a gas, liquid and solid particle mixed phase material, and under the action of the gas phase pressure at the top of the reactor 1ARE, the material goes upward through a product guide pipe 157 inserted below the liquid surface of the liquid collection cup 1AV and is discharged out of the reactor 1ARE as a combined net product of the combined reaction section to enter a downstream processing flow.
As shown in FIG. 1, in the reactor 1BRE system, the mixture 1BF of coal slurry and hydrogen fed via line 111 is mixed with the circulating liquid phase 1BRL1 (which may contain a gas phase and contains liquid phase products from 1ARE and 1 BRE) fed via line 169 to form a mixed material 1BTF, which is fed via line 172 into the bottom of the reactor 1BRE and is usually predistributed via a feed distributor 1BTFS (not shown) installed above the bottom feed inlet of the reactor to distribute the feed as evenly as possible over the entire horizontal feed cross-section of the distribution tray 1 BS; the gas, liquid and solid particle mixed phase material from the lower part of the distribution plate 1BS flows upwards through the distribution plate 1BS, and is subjected to coal hydrogenation direct liquefaction reaction in the ascending process of the main reaction space of the reactor 1BRE to be converted into a top product 1BRTP of the reactor 1 BRE.
As shown in FIG. 1, the difference from the conventional flow scheme shown in FIG. 1 is that the top product 1BRTP is introduced into the partial liquid-removing space composed of the reactor top wall and the liquid-collecting cup 1AV in the upper part of the reactor 1ARE through the pipe 181, mixed with the product 1ARP from the reactor 1ARE, and then subjected to partial liquid-removing. As shown in FIG. 1, the liquid in the top mixed product preferentially settles into the collection cup 1AV under the action of gravity, bubbles are gradually removed in the descending process of the interior of the collection cup 1AV, the circulating liquid phase 1ARL with bubbles removed enters the conduit 1AVP at the bottom of the collection cup 1AV to flow downwards to be discharged out of the reactor, enters the circulating pressure pump 1APUMP through the pipeline 158, and the pressurized second circulating liquid phase 1BRL1 is conveyed through the pipeline 169, then is mixed with the mixture 1BF to form a mixed material 1BTF, and is conveyed into the reactor 1BRE through the pipeline 172 to be circularly processed.
As shown in FIG. 1, the reactor 1ARE is provided with a collection cup 1AV and operates with a circulating liquid phase, i.e., with circulating liquid phase 1ARL1, with or without circulating liquid phase 1BRL1 being used with the reactor 1 BRE.
The flow scheme of the conventional technical scheme shown in figure 1 is suitable for large-scale processing, namely, the situation that at least one reactor in 2 reactors has a large diameter, but for medium-scale and small-scale processing, namely, the situation that the diameter of 2 reactors is small, the defects of large number and small number of reactors are caused, the flow scheme is complex, and the investment is large.
FIG. 2 is a schematic diagram showing a first typical structure and system flow of a reactor having internal parallel reaction zones according to the present invention, which is also a basic flow of the present invention, and can be used in a direct coal hydrogenation liquefaction reaction process, and FIG. 2 shows a case where 2 internal parallel reaction zones are provided in a lower space of a reactor 1 RE. The reactor 1RE may be provided with a plurality of internal parallel reaction zones for receiving a plurality of feeds, as required, and the operating conditions of each coal slurry may be different from one another, and it is generally preferred that the reaction temperatures of the parallel reaction zones are close to each other.
As shown in fig. 2, the combined reactor 1RE includes a bottom shell, a first reaction zone 1ARE, a second reaction zone 1BRE, and a top shell, wherein the reactor shell is provided with 2 bottom feed inlets, 1 top product outlet, 1 collection cup, and 1 collection liquid outlet, and the reactor is internally provided with a first distribution tray and a second distribution tray.
As shown in FIG. 2, in the combined reactor 1RE system, in the first reaction zone 1ARE system, the mixture 1AF of the first coal slurry and hydrogen, which is fed through the line 151, is mixed with the circulating liquid phase 1ARL1 (which may contain a gas phase) fed through the line 159 to form a mixed material 1ATF, which is fed through the line 152 into the bottom of the reactor 1RE, and is pre-distributed through a feed distributor 1ATFS (not shown in the figure) installed above the feed inlet at the bottom of the reactor so that the feed is distributed AS evenly AS possible over the entire horizontal feed cross section of the first distribution tray 1 AS; the 1ATFS feed distributor may be of any suitable construction, such as a perforated or slotted distribution tube, a perforated or slotted distribution cap; distribution tray 1AS, which may be of any suitable construction, typically a plurality of distribution units 1ASK are used, each distribution unit 1ASK being provided with a lower feed line (not shown) of distribution tray 1AS and an upper blister (not shown) of distribution tray 1AS, the gas, liquid and solid particulate mixed phase material from the lower part of distribution tray 1AS passing through distribution tray 1AS via the lower feed line of distribution tray 1AS and entering the upper blister of distribution tray 1AS, then the mixture passes through a gap between a bubble cap at the upper part of the distribution tray 1AS and a feeding pipe at the lower part of the distribution tray 1AS and penetrates through the upper section pipe section of the distribution tray 1AS to be sprayed to the upper end surface of the distributor, and then the mixture flows upwards after being dispersed, collided, mixed and turned, the coal hydrogenation direct liquefaction reaction 1ARE-R is carried out in the ascending process of the main reaction space in the lower end of the reactor, namely the 1ARE section, and is converted into the upper product 1ARE-P of the reaction area 1 ARE.
As shown in fig. 2, in the combined reactor 1RE system, in the second reaction zone 1BRE system, the second slurry oil 1BF delivered through the pipe 171 is mixed with the circulating liquid phase 1BRL1 (which may contain a gas phase) delivered through the pipe 169 to form a mixed material 1BTF, which is delivered through the pipe 172 to enter the second reaction zone 1BRE inside the reactor 1RE, and is usually pre-distributed through a feed distributor 1BTFs (not shown in the figure) installed at the upper part of the feed inlet at the bottom of the reactor to distribute the feed as evenly as possible over the entire horizontal feed section of the first distribution tray 1 BS; the 1BTFS feed distributor may be of any suitable construction, such as a perforated or slotted distribution tube, a perforated or slotted distribution cap; distribution tray 1BS, which may be of any suitable construction, typically employs a plurality of distribution units 1BSK, each distribution unit 1BSK having a lower feed line (not shown) of distribution tray 1BS and an upper blister pocket (not shown) of distribution tray 1BS, the gas, liquid, and solid particulate mixed phase material from the lower portion of distribution tray 1BS passing through distribution tray 1BS via the lower feed line of distribution tray 1BS and entering the upper blister pocket of distribution tray 1BS, then the mixture passes through a gap between a bubble cap at the upper part of the distribution tray 1BS and a feeding pipe at the lower part of the distribution tray 1BS and penetrates through an upper section pipe section of the distribution tray 1BS to be sprayed to the upper end surface of the distributor, and then the mixture flows upwards after being dispersed, collided, mixed and turned, the coal hydrogenation direct liquefaction reaction 1BRE-R is carried out in the ascending process of the main reaction space in the lower end of the reactor, namely the 1BRE section, and is converted into the upper product 1ARE-P of the reaction area 1 BRE.
As shown in fig. 2, the products 1ARE-P, 1ARE-P of the first reaction zone 1ARE, the second reaction zone 1BRE, operated in parallel, ARE typically mixed and reacted during the upward travel of space 1CRE above the parallel reaction zones to convert to a top product 1RE-P, the volume of space 1CRE accounts for a proportion 1CK of the total reaction space volume of the reactor 1RE as a whole, the proportion 1CK being low if space 1CRE performs only mixing tasks, the proportion 1CK being high if space 1CRE performs more deep reaction tasks of mixing materials, and space 1CRE may receive a third hydrocarbon-containing liquid feed to reactor 1 RE.
As shown in FIG. 2, the top product 1RE-P passed through the annular gap between the inner wall of the upper part of the reactor 1RE and the outer wall of the liquid collecting cup 1V and entered the partial liquid removing space consisting of the reactor top wall and the liquid collecting cup 1V in the upper part of the reactor 1 RE. As shown in FIG. 2, the liquid in the top product preferentially settles into the collection cup 1V under the action of gravity, bubbles are gradually removed in the descending process of the interior of the collection cup 1V, the bubble-removed circulating liquid phase 1RL enters the conduit 1VP at the bottom of the collection cup 1V and flows downwards to be discharged out of the reactor, enters the circulating pressure PUMP 1PUMP through the pipeline 158, the pressurized circulating liquid phase 1ARL1 is conveyed through the pipeline 159 and then mixed with the mixture 1AF to form a mixture 1ATF, and the pressurized circulating liquid phase 1BRL1 is conveyed through the pipeline 169 and then mixed with the material 1BF to form a mixture 1 BTF.
As shown in FIG. 2, the top product 1RE-P is separated into a circulating liquid phase 1RL and a net product 1ARTP, the net product 1ARTP is a gas, liquid and solid particle mixed phase material, and under the action of the gas phase pressure at the top of the reactor 1RE, the gas phase material is upwards discharged out of the reactor 1RE through a product guide pipe 157 inserted below the liquid surface of the liquid collecting cup 1V and enters a downstream processing flow.
As shown in FIG. 2, reactor 1RE was equipped with collection cup 1V and operated with circulating liquid phase, i.e., circulating liquid phase 1ARL 1; reactor 1RE may or may not use a recycle liquid phase 1BRL1, as desired.
The first typical flow scheme of the present invention, as shown in fig. 2, can be used in a kerosene co-refining apparatus, and has the following advantages:
compared with 2 sets of independent reactor systems shown in figure 1, the process of the invention shown in figure 2 has the advantages that RE can realize the upsizing of 2 parallel small reactors, thereby reducing the number of reactors, simplifying the reaction system and saving the investment, and therefore, the process has economical efficiency;
secondly, 1RE can effectively utilize the total height of the reactors 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.
FIG. 3 is a schematic diagram of a second exemplary configuration and system flow for a reactor of the present invention having internal parallel reaction zones, which may be used in a kerosene co-refining process, differing from the reactor configuration shown in FIG. 2 only in that: the second reaction zone 1BRE is arranged in parallel in the middle space of the reactor, and the second raw material inlet is positioned on the side wall. The second feedstock 1BF is predistributed by means of an initial distributor 1BTFS (not shown in the figure) when it is injected into the reactor space in such a way that the feed is distributed as evenly as possible over the entire horizontal cross section of the reaction space 1 BRE. The reactor may be provided with a plurality of internal parallel reaction zones for receiving a plurality of feeds, as desired, and the operating conditions of each coal slurry may vary, and it is generally preferred that the reaction temperatures of the parallel reaction zones are close to each other.
FIG. 4 is a schematic diagram of a third exemplary configuration and system flow for a reactor of the present invention having internal parallel reaction zones, which may be used in a kerosene co-refining process, differing from the reactor configuration shown in FIG. 2 only in that: a second distributor is arranged at the middle upper part of the reactor so as to uniformly mix products of 2 internal parallel reaction zones, and a combined reaction zone 1CRE is formed at the spatial position at the upper part of the second distributor; in this case, the reactor 1RE is equivalent to combining 3 small-scale reactions, and has the following advantages:
RE realizes the large-scale of 3 small reactors to reduce the number of reactors, thereby simplifying the flow and saving the investment;
RE can effectively utilize the total height of the reactors 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.
FIG. 5 is a schematic diagram of a fourth exemplary configuration and system flow for a reactor of the present invention having internal parallel reaction zones, which may be used in a kerosene co-refining process, differing from the reactor configuration shown in FIG. 4 only in that: below the second distributor of the reactor, a third feed inlet at the side wall is added for feeding the third feed 1CF from the pipe 131.
As shown in FIG. 5, a third feed 1CF from line 131 enters the reactor RE system to mix with the products of 2 parallel reactors of reactor RE; if desired, the third feedstock 1CF is predistributed by means of an initial distributor 1CTFS (not shown in the figure) when it is injected into the reactor space so that the feed is distributed as evenly as possible over the entire horizontal feed cross-section of the second distribution plate 1 BS.
FIG. 6 is a schematic diagram of a fifth exemplary configuration and system flow for a reactor of the present invention having internal parallel reaction zones, which may be used in a kerosene co-refining process, differing from the reactor configuration shown in FIG. 5 only in that: below the second distributor of the reactor, at the third feed inlet in the side wall, the third feed 1CF from line 131 is introduced into reaction zone 1BRE instead of directly into mixing space 1CRE, first mixed with the feed in reaction zone 1BRE and then mixed with the reaction zone 1ARE product.
The combined reactor can be combined with a downstream and/or an upstream reactor into a complete coal hydrogenation direct liquefaction reaction process according to needs.
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 range as referred to herein refers to the conventional boiling range of the distillate fraction.
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-based values unless otherwise specified.
The conventional gas 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, which is a naphtha component, referred to herein is 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 refers to hydrocarbons with the conventional boiling point of 330-530 ℃.
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 ℃.
The hydrogen-donating hydrocarbon is described below.
The hydrogen donor hydrocarbon refers to a hydrocarbon component having a hydrogen donor function in the coal hydrogenation direct liquefaction process RU, 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 coal hydrogenation direct liquefaction process RU. In the hydrogen supply hydrocarbon, the hydrogen supply speed of a dihydro body is higher than that of a tetrahydro body, and the hydrogen supply speed of the dihydro body of tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of 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:
dissolving, pyrolyzing and liquefying: 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 a solvent hydrogenation extraction liquefaction method: if solvent refining coal methods I and II (SRC-I and SRC-II), hydrogen supply solvent method EDS, 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 oil 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;
coal and residual oil combined processing method (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;
underground liquefaction: 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;
the dry distillation liquefaction method comprises the following steps: the coal is pyrolyzed to obtain tar, and then the tar is subjected to hydrocracking and quality improvement.
The coal hydrogenation direct liquefaction process RU is described below.
The invention discloses a direct coal hydrogenation liquefaction process RU, which refers to 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 modification in the hydrogenation stabilization process, and various processes can be performed according to the difference of the solvent oil and a catalyst and the difference of hydrogenation process conditions, such as the following processes:
the solvent hydrogenation extraction liquefaction method comprises the following steps: if solvent refining coal methods I and II (SRC-I and SRC-II), hydrogen supply solvent method EDS, 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 oil has obvious effect;
② high-pressure catalytic hydrogenation method: 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;
③ a coal and residual oil combined processing method (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;
fourthly, the direct liquefaction method of the China Shenhua group coal;
the patent CN100547055C discloses a hot-melt catalysis method for preparing liquid fuel from lignite, belonging to the direct liquefaction process of lignite by medium-pressure hydrogenation, comprising two processes of coal liquefaction reaction and coal liquefaction oil hydrogenation modification. 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 RU, no matter what kind of direct coal hydrogenation liquefaction process, the aim is to obtain an oil product, the sought function is coal-to-oil, the necessary chemical change is coal hydrogenation, the common characteristics of the prior art are that solvent oil and a catalyst are used, the conventional boiling range of the solvent oil is generally 200-530 ℃, most of the solvent oil is 200-450 ℃, the best of the solvent oil 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 invention discloses a direct coal hydrogenation liquefaction process RU, which 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 hydrogenation 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 RU in the direct coal hydrogenation liquefaction reaction process is normally operated, the hydrogenated modified oil of the coal liquefied oil (usually distillate oil with a conventional boiling range higher than 165 ℃) produced in the direct coal hydrogenation liquefaction reaction process is usually adopted as the hydrogen supply solvent oil, and the main objective of the hydrogenation modification process of the coal liquefied oil is to produce the solvent oil for the RU in the direct coal hydrogenation liquefaction reaction process, specifically, to improve the content of the components with good hydrogen supply function in the oil product, such as the content of the naphthenic benzenes and the dicycloalkylbenzenes, and 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 hydrogenation modification process of the coal liquefied oil is a hydrogenation process with moderate aromatic hydrocarbon saturation.
The final goal of the coal liquefaction reaction process is to produce oil products for external supply, and generally, 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 RU, a hydrogen supply solvent is essentially the most main foreground catalyst of the coal liquefaction positive reaction, rapidly provides most active hydrogen in the coal liquefaction process, and directly determines the rapid hydrogenation stable speed of pyrolysis free radical fragments, thereby inhibiting the thermal condensation reaction; in the process RU of the direct coal hydrogenation liquefaction reaction, solid catalysts such as pyrite, molybdenum sulfide and the like are more similar to a retarder of a 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 RU, solid catalysts such as pyrite, molybdenum sulfide and the like are essentially simultaneously used as recovery catalysts of a hydrogen donor dehydrogenation product SH-Z, and 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 supply 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 RU, 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 RU, the solid catalyst such as pyrite and molybdenum sulfide is more like a background-running catalyst, and plays a supporting and promoting role in coal liquefaction target product distillate oil. In the reaction process RU for preparing the oil by coal hydrogenation, the operation condition and the effect of the hydrogenation stabilization reaction process of the solvent oil are naturally extremely important because the function of the hydrogen donor solvent DS is very important.
In the upflow hydrogenation reactor, the macroscopic flow leading direction of the process medium in the reaction space or the hydrogenation catalyst bed layer is from top to bottom.
The expanded bed reactor is a vertical up-flow reactor, and belongs to an expanded 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 in the reaction process from bottom to top to pass through the reaction space or the catalyst bed layer or flow in the same direction with the upward catalyst; the expanded bed means that a catalyst bed layer is in an expanded 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 working state when a reaction material passes through the catalyst bed layer and the height CUH of an empty bed standing state of the catalyst bed layer, generally, when the KBED is lower than 1.10, the bed is called a micro-expanded bed, when the KBED is between 1.25 and 1.55, the bed is called an ebullated bed, and a suspended bed is considered as the most extreme form of the expanded bed.
The back-mixing flow expanded bed reaction zone refers to the operation mode of the reaction zone of the 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 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 suspended bed reactor of the invention can be in any suitable structural form, can be an empty cylinder suspended bed reactor to form piston flow or back mixing flow with internal circulation, can be an internal circulation guide cylinder to form internal circulation flow or internal external circulation flow, can be a back mixing flow type using an external circulation pipe to make liquid in an upper reaction space flow into external circulation flow of a lower reaction space former, and can be a back mixing flow type using a top product liquid collecting and guide system to form forced internal circulation flow through a circulation pressurization system.
The thermal high separator refers to a gas-liquid separation device for separating intermediate products or final products of hydrogenation reaction.
The direct coal hydrogenation liquefaction reaction process RU generally uses an upflow reactor, and the working mode can be selected as follows:
firstly, a suspension bed hydrogenation reactor;
the fluidized bed hydrogenation reactor discharges the catalyst with reduced activity from the bottom of the bed layer in an intermittent mode, and replenishes fresh catalyst from the upper part of the bed layer in an intermittent mode to maintain the bed layer catalyst inventory;
③ a micro-expansion bed.
The reactor used in the high aromatic hydrogenation thermal cracking reaction process BR of the invention has the working modes that:
firstly, a suspension bed hydrogenation reactor;
a fluidized bed hydrogenation reactor, wherein the catalyst with reduced activity is usually discharged from the bottom of a bed layer in an intermittent mode, and fresh catalyst is supplemented from the upper part of the bed layer in an intermittent mode to maintain the catalyst inventory of the bed layer;
thirdly, an up-flow micro-expansion bed;
fourthly, an up-flow fixed bed;
fifthly, a down-flow fixed bed;
and sixthly, the liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
The solvent oil hydrogenation stable reaction process CR of the invention uses a reactor, and the working mode can be selected as follows:
firstly, a suspension bed hydrogenation reactor;
a fluidized bed hydrogenation reactor, wherein the catalyst with reduced activity is usually discharged from the bottom of a bed layer in an intermittent mode, and fresh catalyst is supplemented from the upper part of the bed layer in an intermittent mode to maintain the catalyst inventory of the bed layer;
thirdly, an up-flow micro-expansion bed;
fourthly, an up-flow fixed bed;
fifthly, a down-flow fixed bed;
and sixthly, the liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
The oil product obtained by directly liquefying coal through hydrogenation comprises naphtha (a fraction with a conventional boiling range of 60-180 ℃), first light diesel oil (a fraction with a conventional boiling range of 180-220 ℃), second light diesel oil (a fraction with a conventional boiling range of 220-265 ℃), heavy diesel oil (a fraction with a conventional boiling range of 265-350 ℃), light wax oil (a fraction with a conventional boiling range of 350-480 ℃), heavy wax oil (a fraction with a conventional boiling range of 480-530 ℃), and liquefied residual oil (hydrocarbons with a conventional boiling point higher than 530 ℃).
Naphtha (fraction with a conventional boiling range of 60-180 ℃) in the coal liquefaction product is a target product fraction, and deep hydrofining such as desulfurization and denitrification can be performed on the naphtha as required, and the benzene ring hydrogenation saturation reaction is generally expected to occur as little as possible.
The first light diesel oil (the fraction with the conventional boiling range of 180-220 ℃) in the coal liquefaction product is not suitable for entering the direct coal hydrogenation liquefaction reaction process RU, because the boiling point is too low and the first light diesel oil is easy to vaporize and is difficult to serve as a liquid phase solvent component; if entering the direct coal hydrogenation liquefaction reaction process RU, the products of the further thermal cracking reaction generate a large amount of gas and are not economical; therefore, unless the value of the gaseous hydrocarbon is huge, the first light diesel oil is generally not suitable to enter the coal hydrogenation direct liquefaction reaction process RU or a special hydrocracking process or a hydrocracking process or other thermal cracking processes for processing, and can generally enter a hydrofining reaction process for desulfurization and denitrification to produce clean light diesel oil.
The second light diesel oil (the fraction with the conventional boiling range of 220-265 ℃) in the coal liquefaction product is a hydrogenation stable oil product which is hydrogen supply solvent oil with proper boiling point and excellent hydrogen supply capability required by the coal hydrogenation direct liquefaction reaction process RU, and in addition, for the coal hydrogenation direct liquefaction process RU, the second light diesel oil or the hydrogenation stable oil thereof, plays a role of a liquid phase basic solvent component in the front reaction process of the coal hydrogenation direct liquefaction reaction process RU, but most of the coal is vaporized in the rear reaction process of the coal hydrogenation direct liquefaction reaction process RU, and generally, the coal hydrogenation direct liquefaction reaction process RU has surplus resources, so the coal hydrogenation direct liquefaction reaction process RU belongs to a main product of the coal hydrogenation direct liquefaction reaction process RU, therefore, the second light diesel oil or the hydrogenated stabilized oil thereof which is the coal liquefaction product is usually partially used as the light hydrogen supply solvent oil to be used in the coal hydrogenation direct liquefaction reaction process RU, and partially used as the hydrogenation quality-improving raw material to be used in the hydrogenation quality-improving reaction process to produce the final product.
The heavy diesel oil (fraction with the conventional boiling range of 265-350 ℃) in the coal liquefaction product is a hydrogen supply solvent oil with proper boiling point and excellent hydrogen supply capacity which is most needed in the coal hydrogenation direct liquefaction reaction process RU, and in addition, the heavy diesel oil or the hydrogen supply stable oil thereof plays a role of a liquid phase basic solvent component in the whole flow of the coal hydrogenation direct liquefaction reaction process RU, and the residual resources exist in the coal hydrogenation direct liquefaction reaction process RU generally, so the heavy diesel oil or the hydrogen supply stable oil thereof belongs to a main product of the coal hydrogenation direct liquefaction reaction process RU, therefore, part of the heavy diesel oil or the hydrogen supply stable oil thereof in the coal liquefaction product is generally used as the heavy hydrogen supply solvent oil in the coal hydrogenation direct liquefaction reaction process RU, and part of the heavy diesel oil or the hydrogen supply stable oil thereof is used as a hydrogen upgrading raw material in the hydrogen upgrading reaction process to produce a final product.
The light wax oil (the fraction with the conventional boiling range of 350-480 ℃) in the coal liquefaction product is a hydrogen supply solvent oil with proper boiling point and excellent hydrogen supply capacity which is most needed in the coal hydrogenation direct liquefaction reaction process RU, and in addition, for the coal hydrogenation direct liquefaction process RU, the light wax oil or the hydrogen supply stable oil thereof plays a role of a liquid phase basic solvent component at the last high-temperature stage of the coal hydrogenation direct liquefaction reaction process RU, and is usually a scarce resource which is difficult to balance by the coal hydrogenation direct liquefaction reaction process RU, therefore, the coal liquefaction product light wax oil or the hydrogen supply stable oil thereof is usually completely used as the heavy hydrogen supply solvent oil for the coal hydrogenation direct liquefaction reaction process RU, and simultaneously, the hydrogenation thermal cracking reaction which is needed in the light-to-weight 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 containing solid particles and materials seriously lacking hydrogen must be carried out under a liquid phase condition rich in hydrogen-supplying hydrocarbon and capable of providing a large amount of active hydrogen atoms so as not to be rapidly coked to maintain 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 dissolved by means of the dispersion of a large amount of hydrogen-supplying hydrocarbon, a thermal condensation compound or a coking substance of the coal liquefaction heavy wax oil also needs to be dispersed and carried out of a reaction space by taking liquefied semicoke as an aggregation carrier, therefore, the deep conversion of the coal liquefied heavy wax oil entering the direct coal hydrogenation liquefaction reaction process RU is a reasonable inevitable choice, or the hydrogenation stable oil obtained by the coal liquefaction heavy wax oil through the hydrogenation stable reaction process enters the coal hydrogenation direct liquefaction reaction process RU for deep conversion, which is a reasonable inevitable choice; in addition, for the coal hydrogenation direct liquefaction process RU, the heavy wax oil or the hydrogenation stable oil thereof plays a role of a liquid phase basic solvent component at the last high temperature stage of the coal hydrogenation direct liquefaction reaction process RU, and is usually a scarce resource which is difficult for the coal hydrogenation direct liquefaction reaction process RU to balance by itself, so that the coal liquefaction product heavy wax oil or the hydrogenation stable oil thereof is usually completely used as the heavy hydrogen supply solvent oil for the coal hydrogenation direct liquefaction reaction process RU, and simultaneously hydrogenation thermal cracking reaction required by the lightening process is carried out.
Since 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 tower, the hydrocarbons, namely the liquefied residual oil, are usually discharged out of the system and are not recycled, and of course, part of the hydrocarbons can be recycled to the RU as required.
The characteristic parts of the present invention are described below.
The invention relates to a coal hydrogenation direct liquefaction reaction process using a reactor with internal parallel reaction zones, which is characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and possibly catalyst, coal slurry containing coal dust is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least 1 reaction section, including at least one reaction section using a reactor with internal parallel reaction zones;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation uses the upflow reactor KRE with the internal parallel reaction zone, at least 2 parallel reaction zones KARE and reaction zones KBRE are separated in the reaction space of the reactor KRE, a liquid collecting cup and a collected liquid guiding-out system are arranged in the liquid separating space at the top of the reactor KRE, and the working mode is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
a material based on the mixture MP-TO-TS, used as top wet space feedstock 100F;
in a liquid separation space formed by a reactor top shell and a liquid collecting cup at the top of the reactor KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products;
and fifthly, in a liquid material circulating system, at least one part of collecting liquid KRE-RL is pressurized by a circulating pump and then returns to the reaction space of the reactor KRE for circulating processing.
The invention generally sets up a mixed reaction zone KCRE, which is characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and possibly catalyst, coal slurry containing coal dust is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least 1 reaction section, including at least one reaction section of a reactor with an internal parallel reaction zone;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation has upflow reactor KRE of inside parallel reaction zone, cuts out 2 at least parallel reaction zone KARE and reaction zone KBRE in reactor KRE's reaction space, divides the liquid space and sets up liquid collecting cup and collection liquid derivation system in reactor KRE's top, and its working method is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
performing at least one part of coal hydrogenation direct liquefaction reaction on the mixture MP-TO-TS-based material TO convert the mixture MP-TO-TS into a mixed reaction zone product KCRE-P;
at least a portion of the mixed reaction zone product KCRE-P is used as top liquid space feed 100F;
and fourthly, in a liquid separation space formed by the top shell of the reactor and the liquid collecting cup at the top of the KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products.
In the present invention, generally, in a liquid circulation system of the reactor KRE having the reaction zones connected in parallel therein, at least a part of the collected liquid KRE-RL is pressurized by the circulation pump and then returned to the reaction zone KARE of the reactor KRE or/and the reaction zone KBRE for circulation processing.
In the invention, generally, the reactor KRE with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the upward reaction material refers to the reaction material flowing upward in the main direction in the reactor KRE.
In the present invention, generally, in a reactor KRE having internal parallel reaction zones, respective ascending reaction material distributors are provided in the parallel reaction zones, and an ascending reaction material distributor is provided in the mixed reaction zone KCRE.
In the invention, generally, inside a KRE (KRE) internally connected with a reaction zone in parallel, respective ascending reaction material distributors are arranged in the reaction zone in parallel, and an ascending reaction material distributor is arranged in a KCRE (KCRE) mixing reaction zone, thereby forming material distributors arranged in series;
a material input pipe containing a liquid raw material introduction space DH is arranged in a space DH between the lower section distributor and the upper section distributor and at a position close to the upper section distributor;
the upward reaction material refers to a reaction material flowing upwards in the main body direction in the KRE reactor;
the cross-section distributor refers to a material distributor which is horizontally arranged in the reactor KRE and can evenly distribute the ascending material from the lower space of the reactor KRE to the upper reaction space of the distributor.
According to the invention, in the direct coal hydrogenation liquefaction reaction process RU, slurry containing materials based on KRE products of reactors in parallel connection with reaction zones inside enter the downstream direct coal hydrogenation liquefaction reaction process to carry out deep coal liquefaction reaction;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by coal hydrogenation direct liquefaction reaction.
According to the invention, in the direct coal hydrogenation liquefaction reaction process RU, slurry-containing slurry feeding of a reactor KRE in an internal parallel reaction area is slurry-containing material based on the product of an upstream direct coal hydrogenation liquefaction reactor;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by the direct liquefaction reaction of coal hydrogenation.
In the present invention, usually, the liquid circulation system of the reactor KRE is connected in parallel with the inside of the reactor KRE, and at least a part of the collected liquid KRE-RL is pressurized by the circulating pump and then returned to the reaction zone KARE of the reactor KRE or/and the reaction zone KBRE for circulation processing.
In the invention, generally, a liquid material circulating system of the reactor KRE in a reaction zone is connected in parallel inside, at least one part of collected liquid KRE-RL is pressurized by the same 1 circulating pump and then divided into at least 2 circulating materials, and each circulating material enters different reaction zones of the reactor KRE for circulating processing.
In the present invention, the operation mode of the KRE reactor with parallel reaction zones inside can be selected from 1 or more of the following:
firstly, a suspension bed reactor;
② a fluidized bed reactor;
and thirdly, a suspended bed and a fluidized bed reactor, wherein a fluidized bed reaction zone is arranged in the reaction space of the suspended bed.
According to the invention, the liquid material entering the reactor KRE of the internal parallel reaction zone can be selected from 1 or more of the following liquid materials:
oil coal slurry or coal liquefaction intermediate product slurry is subjected to coal hydrogenation direct liquefaction reaction in the coal hydrogenation direct liquefaction reaction process;
secondly, under the condition that one path of liquid material is ensured to be oil coal slurry or coal liquefaction intermediate product slurry, the other path of liquid material is distilled oil which is directly liquefied and reacted to generate oil based on coal hydrogenation, and hydrogenation thermal cracking reaction is carried out in a KRE reactor;
thirdly, under the condition that one path of liquid material is oil coal slurry or coal liquefaction intermediate product liquid material, performing hydrogenation stabilization reaction based on the distilled oil generated by the direct liquefaction reaction of coal hydrogenation in the hydrogenation stabilization reaction process MR to produce hydrogen supply solvent oil required by the direct liquefaction reaction process of coal hydrogenation, wherein the hydrogen supply solvent oil enters a reactor KRE to participate in the coal liquefaction reaction;
and fourthly, under the condition that one path of liquid material is ensured to be the coal oil slurry or the coal liquefaction intermediate product slurry, the other path of liquid material is non-coal-based heavy oil, and the coal oil is formed.
According to the invention, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering the reaction zone KARE contains oil coal slurry or coal liquefaction intermediate product slurry;
in the reactor KRE internally connected in parallel with the reaction zone, the material KF2 entering the reaction zone KBRE contains coal oil slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil.
According to the invention, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering a KARE reaction zone contains oil coal slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil;
in the reactor KRE with parallel reaction zones inside, the material KF2 entering the reaction zone KBRE contains oil coal slurry or coal liquefaction intermediate product slurry.
The invention discloses a coal hydrogenation direct liquefaction reaction process RU, which comprises at least 2 reaction sections of slurry material serial operation, wherein the first reaction section is a reaction section formed by reactors with internal parallel reaction zones, and the flow mode of the coal hydrogenation direct liquefaction reaction process RU can be selected from 1 or more of the following steps:
the method comprises the following steps that firstly, a coal hydrogenation direct liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid phase from the first reaction section;
a second reaction section is set, and an up-flow type expanded bed coal hydrogenation direct liquefaction reactor 2RE is used; the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is used as lower feed to enter the lower part of the reactor 2RE and flow upwards to pass through the main reaction area, and is converted into a reaction product 2RTP to be discharged out of the reactor 2 RE;
the direct coal hydrogenation liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid material 1ALPA mainly comprising solid-liquid-containing materials in weight from the first reaction section;
setting up a second reaction section, using an upflow expanded bed coal hydrogenation direct liquefaction reactor 2RE, feeding a product liquid material 1ALPA of the first reaction section as a lower feed into the lower part of the reactor 2RE to flow upwards to pass through the main reaction area, converting the product into a reaction product 2RTP and discharging the reaction product 2 RE;
meanwhile, the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is taken as an upper feed to enter the upper part of the reactor 2RE and is mixed and contacted with the materials in the reactor 2 RE;
the reactor 2RE is provided with a top liquid collecting cup, and the collected liquid is circularly returned to the lower reaction space of the reactor 2RE for circular processing;
the direct coal hydrogenation liquefaction reaction process RU comprises a pre-hydrogenation reaction section OPRE and a first reaction section which are operated in series;
in the pre-hydrogenation reaction section OPRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction pre-hydrogenation reaction and is converted into a coal hydrogenation direct liquefaction pre-hydrogenation reaction product OPRE-RP, and at least one part of the pre-hydrogenation reaction product OPRE-RP enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction;
the coal hydrogenation direct liquefaction reaction process RU comprises a pre-hydrogenation reaction section OPRE and a first reaction section which are operated in series;
in the pre-hydrogenation reaction section OPRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction pre-hydrogenation reaction and is converted into coal hydrogenation direct liquefaction pre-hydrogenation reaction product OPRE-RP, liquid material OPLPX mainly comprising solid slurry in weight is obtained based on the pre-hydrogenation reaction product OPRE-RP, and at least a part of the liquid material product OPLPX enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction.
According to the invention, in the general process of direct coal hydrogenation liquefaction reaction RU, the conversion rate of the anhydrous and ashless components of the raw material coal is 70-98%.
According to the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the coal slurry raw material is processed, and simultaneously, the non-coal-based heavy oil is processed, wherein the conversion rate of the hydrogenation thermal cracking reaction of the non-coal-based heavy oil is 40-90%.
In the invention, in general, in a reactor KRE internally connected with a reaction zone in parallel, a material KF1 entering the reaction zone KARE is thick coal slurry;
in the KRE, a material KF2 entering a reaction zone KBRE is dilute coal slurry, and the absolute difference of the coal concentration of the dilute coal slurry KF2 lower than that of the thick coal slurry KF1 is 5-35%.
According to the invention, usually, dilute coal slurry and thick coal slurry are simultaneously processed in a reactor KRE of an internal parallel reaction zone, wherein the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%.
According to the invention, usually, dilute coal slurry and thick coal slurry are processed simultaneously in a reactor KRE with an internal parallel reaction zone, wherein the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%; the ratio of the weight flow WF2-W of the thick coal slurry WF2 to the weight flow WF1-W of the thin coal slurry WF1 is a slurry ratio K100, K100 is WF2-W/WF1-W, and K100 is 0.01-1.0.
In the invention, generally, in the coal hydrogenation direct liquefaction reaction process RU, the operation conditions of the coal hydrogenation direct liquefaction reaction process to which the pulverized coal is subjected are as follows: the reaction temperature is 400-490 ℃, the reactor pressure is 6-30 MPa, the volume concentration of gas-phase hydrogen is 50-95%, and the gas-liquid ratio is 300-2500 Nm3The addition amount of the direct coal hydrogenation liquefaction catalyst is 0.1-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is that the molar ratio of sulfur in the cocatalyst to the active metal of the catalyst is 1.0-2.0, the solid concentration of the coal slurry is 40-60 mass%, and the reaction retention time is 0.5-4 hours.
In the invention, in the process of the direct coal hydrogenation liquefaction reaction RU, the used direct coal hydrogenation liquefaction catalyst can be a composite hydrogenation catalyst which comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the direct coal hydrogenation liquefaction catalyst is less than 2 wt%; the direct coal hydrogenation liquefaction catalyst is powdery particles with the particle diameter of 1-100 mu m.
According to the invention, in the coal hydrogenation direct liquefaction reaction process RU, the coal hydrogenation direct liquefaction catalyst used can be a nanometer ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
In the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the hydrogen-donating solvent oil contained in the coal slurry feed mainly comprises hydrocarbons with the conventional boiling point of 250-530 ℃.
In the invention, generally, in the direct coal hydrogenation liquefaction reaction process RU, the ratio of the weight of the hydrogen donor solvent DS to the weight of the coal powder is 0.5-2.0 calculated by all the fed materials.
In the invention, in general, in the direct coal hydrogenation liquefaction reaction process RU, at least one of the raw materials containing liquid hydrocarbons mainly contains a hydrogen donor, wherein the hydrogen donor mainly comprises hydrocarbons with a conventional boiling point of 250-530 ℃, the weight content of part of saturated aromatic hydrocarbons in the hydrogen donor is more than 15%, and the aromatic carbon rate is 0.35-0.70.
In the invention, in the process of direct coal hydrogenation liquefaction reaction RU, at least one part of slurry blending solvent oil contained in the raw material coal slurry can be selected from 1 or more of the following materials:
firstly, middle-low temperature coal tar or distillate oil thereof or oil products obtained in the thermal processing process of the coal tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
② high temperature coal tar or distillate oil thereof or oil product material flow obtained in the thermal processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
③ fractionating oil of the product of the direct coal hydrogenation liquefaction process or oil products obtained in the thermal processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
shale oil or distillate oil thereof or oil products obtained in the thermal processing process of the shale oil or distillate oil; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
ethylene cracking tar or oil products obtained in the thermal processing process of the ethylene cracking tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
oil products obtained in the oil-based heavy oil-heating processing process; the thermal processing process is selected from coking process or catalytic cracking process or hydrogenation process;
seventhly, petroleum sand-based heavy oil or oil products obtained in the thermal processing process of the petroleum sand-based heavy oil; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
other hydrocarbon oils with a content of aromatics higher than 40% by weight.
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 desired, 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 the desired level of 500ppm (v), or 1000ppm (v), or 3000ppm (v), is not below the minimum level required to ensure the required partial pressure of hydrogen sulfide over the catalyst to ensure the required sulfiding 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 generally 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, a hot high-pressure separator with the operation temperature generally being 150-450 ℃ is also needed, at the moment, the hydrogenation reaction effluent enters the hot high-pressure separator to be separated into hot high-molecular gas mainly comprising hydrogen in volume and hot high-molecular oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solids, the hot high-molecular gas enters the cold high-pressure separator with the operation temperature generally being 20-80 ℃ to be separated into cold high-molecular oil and cold high-molecular gas, and as a large amount of high-boiling-point components enter the hot high-molecular oil liquid, the following aims are achieved: 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 reaction effluent or the hot high-pressure gas or the warm high-pressure gas enters the cold high-pressure separation part, the temperature is usually reduced (generally, heat exchange with the reaction part feed) to about 220 to 100 ℃ (the temperature is higher than the crystallization temperature of the ammonium hydrosulfide and the crystallization temperature of the ammonium chloride in the gas phase of the hydrogenation reaction effluent), then washing water is usually injected into the reaction effluent to form the hydrogenation reaction effluent after water injection, 2 or more water injection points may be needed to be arranged, the washing water is used for absorbing ammonia and other impurities such as hydrogen chloride and the like which may be generated, and the water solution after absorbing the ammonia necessarily absorbs the 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 contains 0.5-15% (w), preferably 1-8% (w) of ammonia. 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 yet another 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 preferably not greater than 200ppm (v), and most preferably not greater than 50ppm (v). The operating pressure of the cold high-pressure separator is the difference between the pressure of the hydrogenation reaction part and the actual pressure drop, and the difference between the operating 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%, is returned to the hydrogenation part for recycling so as to provide the hydrogen amount and the hydrogen concentration necessary for the hydrogenation 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, CO2The yield is high, most of cold high-fraction gas is generally about 70-100%, the permeation hydrogen obtained after purification through a membrane separation process is pressurized and then returns to the hydrogenation reaction process, and the non-permeation gas is pressurized and returned to the hydrogenation reaction process for recycling after PSA hydrogen extraction or after 'water vapor conversion hydrogen production + PSA hydrogen extraction'.
Fresh hydrogen is fed into the hydrogenation section to replenish hydrogen consumed during the hydrogenation reaction, and the higher the concentration of fresh hydrogen, the better, the more preferably the concentration of fresh hydrogen is not lower than 95% (v), and the more preferably not lower than 99% (v). All of the fresh hydrogen may be introduced into any of the hydrogenation sections, preferably the first hydrogenation reactor.
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 (27)
1. The direct coal hydrogenation liquefaction reaction process using a reactor with internal parallel reaction zones is characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and catalyst or not, coal slurry containing coal powder is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least one reaction section of a reactor with internal parallel reaction zones;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation uses the upflow reactor KRE with the internal parallel reaction zone, at least 2 parallel reaction zones KARE and reaction zones KBRE are separated in the reaction space of the reactor KRE, a liquid collecting cup and a collected liquid guiding-out system are arranged in the liquid separating space at the top of the reactor KRE, and the working mode is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
a material based on the mixture MP-TO-TS, used as top wet space feedstock 100F;
in a liquid separation space formed by a reactor top shell and a liquid collecting cup at the top of the reactor KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products;
and fifthly, in a liquid material circulating system, at least one part of collecting liquid KRE-RL is pressurized by a circulating pump and then returns to the reaction space of the reactor KRE for circulating processing.
2. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, under the conditions of hydrogen, conventional liquid hydrocarbon and catalyst or not, coal slurry containing coal powder is subjected to at least partial direct coal hydrogenation liquefaction reaction RUR to be converted into a reaction product RUP, and the reaction product RUP is recovered;
the coal hydrogenation direct liquefaction reaction process RU comprises at least one reaction section of a reactor with internal parallel reaction zones;
the reactor with the internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone;
the reaction section refers to a process comprising a coal hydrogenation direct liquefaction reaction step and a gas-liquid separation step of gas-liquid products in the step;
the reaction section K of the direct liquefaction reaction process RU of coal hydrogenation has upflow reactor KRE of inside parallel reaction zone, cuts out 2 at least parallel reaction zone KARE and reaction zone KBRE in reactor KRE's reaction space, divides the liquid space and sets up liquid collecting cup and collection liquid derivation system in reactor KRE's top, and its working method is as follows:
firstly, in a reaction zone KARE, a material KF1 containing a first liquid material KSF1 enters the lower part of the reaction zone KARE to flow upwards in a main flow direction, and at least part of coal hydrogenation direct liquefaction reaction KARE-R is carried out to be converted into a reaction zone product KARE-P;
secondly, in the reaction zone KBRE, the material KF2 containing the second liquid material KSF2 enters the lower part of the reaction zone KBRE to flow upwards in the main flow direction, and at least part of the coal hydrogenation direct liquefaction reaction KBRE-R is carried out to be converted into a reaction zone product KBRE-P;
contacting the product KARE-P with the product KBRE-P in the mixed reaction zone KCRE TO form a mixture MP-TO-TS;
performing at least one part of coal hydrogenation direct liquefaction reaction on the mixture MP-TO-TS-based material TO convert the mixture MP-TO-TS into a mixed reaction zone product KCRE-P;
at least a portion of the mixed reaction zone product KCRE-P is used as top liquid space feed 100F;
and fourthly, in a liquid separation space formed by the top shell of the reactor and the liquid collecting cup at the top of the KRE, carrying out gas-liquid separation on the raw material 100F in the liquid separation space at the top to obtain collecting liquid KRE-RL discharged by the collecting cup and other products.
3. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
at least one part of collected liquid KRE-RL is pressurized by a circulating pump and then returns to the reaction zone KARE or/and the reaction zone KBRE of the reactor KRE for circular processing in a liquid-material circulating system of the reactor KRE with the inner part connected with the reaction zone in parallel.
4. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
the KRE reactor with internal parallel reaction zones comprises a bottom shell, at least 2 parallel reaction zones and a top shell, wherein the reactor shell is provided with a feed inlet, a top product outlet and a collected liquid guide outlet of each parallel reaction zone, and each parallel reaction zone is provided with an ascending reaction material distributor;
the upward reaction material refers to the reaction material flowing upward in the main direction in the reactor KRE.
5. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
inside the reactor KRE with the internal parallel reaction zones, respective ascending reaction material distributors are arranged in the parallel reaction zones, and the ascending reaction material distributors are arranged in the mixed reaction zone KCRE.
6. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
inside KRE inside the reactor with parallel reaction zones, setting respective ascending reaction material distributors in the parallel reaction zones, and setting ascending reaction material distributors in the mixed reaction zone KCRE, thereby forming material distributors arranged in series;
a material input pipe containing a liquid raw material introduction space DH is arranged in a space DH between the lower section distributor and the upper section distributor and at a position close to the upper section distributor;
the upward reaction material refers to a reaction material flowing upwards in the main body direction in the KRE reactor;
the cross-section distributor refers to a material distributor which is horizontally arranged in the reactor KRE and can evenly distribute the ascending material from the lower space of the reactor KRE to the upper reaction space of the distributor.
7. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, slurry materials containing KRE products of the reactors based on the internal parallel reaction zones enter a downstream direct coal hydrogenation liquefaction reaction process to carry out deep coal liquefaction reaction;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by the direct liquefaction reaction of coal hydrogenation.
8. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, the slurry-containing material of the KRE reactor in the internal parallel reaction area is a slurry-containing material based on the product of the upstream direct coal hydrogenation liquefaction reactor;
the material containing slurry refers to a material containing a solid converted substance and a liquid converted substance obtained by the direct liquefaction reaction of coal hydrogenation.
9. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
at least one part of collected liquid KRE-RL is pressurized by a circulating pump and then returns to the reaction zone KARE or/and the reaction zone KBRE of the reactor KRE for circular processing.
10. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
at least one part of collected liquid KRE-RL is pressurized by 1 circulating pump and then divided into at least 2 circulating materials, and each circulating material enters different reaction areas of the reactor KRE for circulating processing.
11. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
the operation mode of the reactor KRE of the internal parallel reaction zone is selected from 1 or more of the following:
firstly, a suspension bed reactor;
② a fluidized bed reactor;
and thirdly, a suspended bed and a fluidized bed reactor, wherein a fluidized bed reaction zone is arranged in the reaction space of the suspended bed.
12. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
the liquid material entering the reactor KRE of the internal parallel reaction zone is selected from 1 or more of the following liquid materials:
oil coal slurry or coal liquefaction intermediate product slurry is subjected to coal hydrogenation direct liquefaction reaction in the coal hydrogenation direct liquefaction reaction process;
secondly, under the condition that one path of liquid material is oil coal slurry or coal liquefaction intermediate product slurry, the other path of liquid material is distilled oil which is generated by direct liquefaction reaction based on coal hydrogenation, and hydrogenation thermal cracking reaction is carried out in a reactor KRE;
thirdly, under the condition that one path of liquid material is oil coal slurry or coal liquefaction intermediate product liquid material, performing hydrogenation stabilization reaction based on distilled oil which is generated by coal hydrogenation direct liquefaction reaction in a hydrogenation stabilization reaction process MR to produce hydrogen supply solvent oil required by the coal hydrogenation direct liquefaction reaction process, wherein the hydrogen supply solvent oil enters a reactor KRE to participate in coal liquefaction reaction;
and fourthly, under the condition that one path of liquid material is ensured to be the coal oil slurry or the coal liquefaction intermediate product slurry, the other path of liquid material is non-coal-based heavy oil, and the coal oil is formed.
13. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the reactor KRE internally connected with the reaction zone in parallel, the material KF1 entering the reaction zone KARE contains oil coal slurry or coal liquefaction intermediate product slurry;
in the reactor KRE internally connected in parallel with the reaction zone, the material KF2 entering the reaction zone KBRE contains coal oil slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil.
14. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the reactor KRE internally connected with the reaction zones in parallel, the material KF1 entering the KARE reaction zone contains coal oil slurry or coal liquefaction intermediate product slurry or solid-containing non-coal-based heavy oil or solid-free non-coal-based heavy oil;
in the reactor KRE with parallel reaction zones inside, the material KF2 entering the reaction zone KBRE contains oil coal slurry or coal liquefaction intermediate product slurry.
15. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
the coal hydrogenation direct liquefaction reaction process RU comprises at least 2 reaction sections of slurry material serial operation, wherein the first reaction section is a reaction section formed by reactors of internal parallel reaction areas, and the flow mode of the coal hydrogenation direct liquefaction reaction process RU is selected from 1 or more of the following reaction sections:
the method comprises the following steps that firstly, a coal hydrogenation direct liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid phase from the first reaction section;
a second reaction section is set, and an up-flow type expanded bed coal hydrogenation direct liquefaction reactor 2RE is used; the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is used as lower feed to enter the lower part of the reactor 2RE and flow upwards to pass through the main reaction area, and is converted into a reaction product 2RTP to be discharged out of the reactor 2 RE;
the direct coal hydrogenation liquefaction reaction process RU comprises 2 reaction sections in which slurry materials are operated in series;
discharging a mixed-phase product 1RTP containing a gas phase and a liquid material 1ALPA mainly comprising solid-liquid-containing materials in weight from the first reaction section;
setting up a second reaction section, using an up-flow expanded bed coal hydrogenation direct liquefaction reactor 2RE, enabling a product liquid material 1ALPA of the first reaction section to enter the lower part of the reactor 2RE as a lower feed to flow upwards to pass through a main reaction area, converting into a reaction product 2RTP and discharging out of the reactor 2 RE;
meanwhile, the mixed-phase product 1RTP containing gas phase and liquid phase in the first reaction section is taken as an upper feed to enter the upper part of the reactor 2RE and is mixed and contacted with the materials in the reactor 2 RE;
the reactor 2RE is provided with a top liquid collecting cup, and the collected liquid is circularly returned to the lower reaction space of the reactor 2RE for circular processing;
the direct coal hydrogenation liquefaction reaction process RU comprises a PRE-hydrogenation reaction section 0PRE and a first reaction section which are operated in series;
in the PRE-hydrogenation reaction section 0PRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction PRE-hydrogenation reaction and is converted into coal hydrogenation direct liquefaction PRE-hydrogenation reaction product 0PRE-RP, and at least a part of the PRE-hydrogenation reaction product 0PRE-RP enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction;
the coal hydrogenation direct liquefaction reaction process RU comprises a PRE-hydrogenation reaction section 0PRE and a first reaction section which are operated in series;
in the PRE-hydrogenation reaction section 0PRE, coal slurry material F1 is subjected to coal hydrogenation direct liquefaction PRE-hydrogenation reaction and is converted into coal hydrogenation direct liquefaction PRE-hydrogenation reaction product 0PRE-RP, liquid material 0PLPX mainly composed of solid-containing slurry is obtained based on the PRE-hydrogenation reaction product 0PRE-RP, and at least a part of the liquid material product 0PLPX enters the reaction space of the reactor 1RE of the first reaction section to be subjected to coal liquefaction reaction.
16. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, the conversion rate of the anhydrous and ashless components of the raw material coal is 70-98%.
17. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, the coal slurry raw material is processed, and simultaneously, the non-coal-based heavy oil is processed, wherein the conversion rate of the hydrogenation thermal cracking reaction of the non-coal-based heavy oil is 40-90%.
18. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in a reactor KRE internally connected with the reaction zones in parallel, a material KF1 entering the reaction zone KARE is thick coal slurry;
in the KRE, a material KF2 entering a reaction zone KBRE is dilute coal slurry, and the absolute difference of the coal concentration of the dilute coal slurry KF2 lower than that of the dense coal slurry KF1 is 5-35%.
19. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the KRE of the reactor with the internal parallel reaction zones, dilute coal slurry and thick coal slurry are processed simultaneously, the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%.
20. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in a KRE reactor with an internal parallel reaction zone, dilute coal slurry and thick coal slurry are processed simultaneously, wherein the coal concentration CA of the dilute coal slurry is 35-50%, and the coal concentration CB of the thick coal slurry is 50-70%; the ratio of the weight flow WF2-W of the thick coal slurry WF2 to the weight flow WF1-W of the thin coal slurry WF1 is a slurry ratio K100, K100 is WF2-W/WF1-W, and K100 is 0.01-1.0.
21. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the coal hydrogenation direct liquefaction reaction process RU, the operation conditions of the coal hydrogenation direct liquefaction reaction process to which the pulverized coal is subjected are as follows: the reaction temperature is 400-490 ℃, the reactor pressure is 6-30 MPa, the volume concentration of gas-phase hydrogen is 50-95%, and the gas-liquid ratio is 300-2500 Nm3The addition amount of the direct coal hydrogenation liquefaction catalyst is 0.1-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is that the molar ratio of sulfur in the cocatalyst to the active metal of the catalyst is 1.0-2.0, the solid concentration of the coal slurry is 40-60 mass%, and the reaction retention time is 0.5-4 hours.
22. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the process of the direct coal hydrogenation liquefaction reaction RU, the used direct coal hydrogenation liquefaction catalyst is a composite hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the direct coal hydrogenation liquefaction catalyst is less than 2 wt%; the direct coal hydrogenation liquefaction catalyst is powdery particles with the particle diameter of 1-100 mu m.
23. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the coal hydrogenation direct liquefaction reaction process RU, the coal hydrogenation direct liquefaction catalyst used is a nanometer ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
24. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, hydrogen supply solvent oil contained in the coal slurry feed mainly comprises hydrocarbons with the conventional boiling point of 250-530 ℃.
25. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, the ratio of the weight of the hydrogen donor solvent DS to the weight of the coal powder is 0.5-2.0 calculated by all the fed materials.
26. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, at least one path of raw materials in all the raw materials containing liquid hydrocarbons contains a hydrogen donor, wherein the hydrogen donor mainly comprises hydrocarbons with the conventional boiling point of 250-530 ℃, the weight content of part of saturated aromatic hydrocarbons in the hydrogen donor is more than 15%, and the aromatic carbon rate is 0.35-0.70.
27. The coal hydrogenation direct liquefaction reaction process of claim 1, characterized in that:
in the direct coal hydrogenation liquefaction reaction process RU, at least one part of slurry blending solvent oil contained in the raw material coal slurry is selected from 1 or more of the following materials:
firstly, middle-low temperature coal tar or distillate oil thereof or oil products obtained in the thermal processing process of the coal tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
② high temperature coal tar or distillate oil thereof or oil product material flow obtained in the thermal processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
thirdly, fractionated oil of a product obtained in the process of direct liquefaction by coal hydrogenation or oil obtained in the process of thermal processing of the product; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
shale oil or distillate oil thereof or oil products obtained in the thermal processing process of the shale oil or distillate oil; the thermal processing process is selected from coking process or catalytic cracking process or hydrogenation process;
ethylene cracking tar or oil products obtained in the thermal processing process of the ethylene cracking tar; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
oil products obtained in the oil-based heavy oil-heating processing process; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
seventhly, petroleum sand-based heavy oil or oil products obtained in the thermal processing process of the petroleum sand-based heavy oil; the thermal processing process is selected from a coking process or a catalytic cracking process or a hydrogenation process;
other hydrocarbon oils with a content of aromatics higher than 40% by weight.
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CN104941526A (en) * | 2014-03-26 | 2015-09-30 | 何巨堂 | Up-flow type reactor |
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CN104941526A (en) * | 2014-03-26 | 2015-09-30 | 何巨堂 | Up-flow type reactor |
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