CN102816596B - Deep processing method of non-caking coal or feebly caking coal - Google Patents
Deep processing method of non-caking coal or feebly caking coal Download PDFInfo
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Abstract
The invention discloses a deep processing method of non-caking coal or feebly caking coal, which comprises the following steps: performing medium-and-low-temperature carbonization reaction on non-caking coal or feebly caking coal to generate coal gas, semicoke and coal tar; treating the coal tar as follows: inputting the coal tar material, oil gas obtained through delayed coking reaction and a hydrocracking liquid-phase product into a distillation tower, and distilling out naphtha fractions, carbolic-oil-containing fractions, wax oil fractions and tower bottom oil; mixing the naphtha fractions with hydrogen, and inputting into a naphtha hydrofining reaction section; dephenolizing the carbolic-oil-containing fractions to obtain dephenolized oil, mixing with the wax oil fractions, and inputting into a hydrotreating reaction section; fractionating the hydrotreating reaction liquid phase into light fractions and heavy fractions, and performing hydrocracking on the heavy fractions; and inputting the tower bottom oil obtained through distillation into a delayed coker. Compared with the prior art, the method disclosed by the invention performs sufficient deep processing on coal, improves the yield of light fuel oil produced from coal tar, and simultaneously prolongs the service life of a catalyst in a hydrogenation device.
Description
Technical field
The present invention relates to Coal Chemical Industry technique, be specifically related to the deep processing method of a kind of dross coal or weak caking coal, belong to coal chemical technology.
Background technology
The shortage of world's crude resources is extremely urgent, and distributed pole is unbalanced, and the storage capacity of coal is very abundant, therefore produces with coal the approach that vehicle fuel oil product are a kind of necessity.Comprise the direct liquefaction of coal and the indirect liquefaction of coal etc. by the major technique of coal liquefaction, but these technical costss are high, technical sophistication.Another is the technology of producing coke, can be in producing coke, and by-product coal tar, this is the method extensively adopting at present.
Dross coal or weak caking coal comprise brown coal, long-flame coal and bottle coal etc.Brown coal are coals that degree of coalification is minimum, its moisture is high, proportion is little, volatile matter is high, non-caked, chemical reactivity strong, poor heat stability, thermal value are low, the humic acid that contains different quantities, be used as the raw material of fuel, gasification more, also can be used to extract montanin wax and humic acid, manufacture sulphonated coal or gac.The volatile content of long-flame coal is also very high, there is no or only have very little cohesiveness, and easy firing has very long flame when burning, therefore the long-flame coal of gaining the name.Long-flame coal can, as the raw material of gasification, also can be used as civilian and power fuel.Bottle coal volatile matter is high, and gelatinous layer is thicker, poor heat stability.Bottle coal coking separately, but the coke of producing is elongated frangible, and shrinking percentage is large, and longitudinal crack is many, anti-crushing poor with wear resistance.So bottle coal can only be used as coal-blending coking, also can be used to manufacture coal gas, produce nitrogenous fertilizer or power fuel.
In the incoherences such as brown coal, long-flame coal and bottle coal or weak caking coal, all contain abundant organic matter, in the time of middle low-temperature pyrolysis, except producing semicoke, also can generate coal gas and coal tar.In China, the incoherences such as brown coal, long-flame coal and bottle coal or weak caking coal are that reserves are abundant but almost also not by the resource of fine utilization.Along with the fast development of China's economy, the demand of the energy is also in continuous expansion.Energy strategy more and more becomes the important component part of China's development strategy.China is an oil starvation, weak breath and country that coal resources enrich relatively, and " oil starvation, weak breath, rich coal " is the fundamental realities of the country of China, and in the fossil energy reserves of verifying, coal accounts for more than 90%.Along with the crude oil demand of the constantly soaring and domestic cumulative year after year of International Crude Oil, domestic petroleum output can not meet the needs of national economy high speed development far away.Therefore, for ensureing the Sustainable development of Chinese national economy, optimize China's energy structure, reduce the interdependency to petroleum import, make full use of the coal resources advantage of China's abundant, greatly develop Coal Chemical Industry new high-tech industry, with Coal Chemical Industry products substitution petrochemicals, become the inevitable choice of China's energy strategy.
The existing industrialization technology that utilizes the incoherences such as brown coal, long-flame coal, bottle coal or weak caking coal has:
1. gasification: gasification is to change coal into can be used as industry or domestic fuel and chemical industry synthesis material coal gas, but gasification is subject to the restriction of the type of furnace, coal, moisture, granularity, can not implement in full.
2. coking: isolated air heats coal, in coal, organic matter raises and is decomposed gradually with temperature, and wherein volatile matter is overflowed with gaseous state or vapor state, become coke-oven gas and coal tar, and non-volatile solids residue is coke.But the incoherences such as brown coal, long-flame coal, bottle coal or weak caking coal can not be separately as coking with coal, and only have bottle coal to can be used as a coal of coke making and coal blending, use range is on the low side.
3. destructive distillation: coal is placed in to destructive distillation at the temperature of 600 DEG C of left and right and can generates tar, coke-oven gas and semicoke.The elementary composition of semicoke is mainly carbon, hydrogen and oxygen, and the nitrogen in raw coal and element sulphur be almost most of consumption in pyrolytic process, and a small amount of nitrogen, element sulphur are present in semicoke with the form of heterogeneous ring compound.In semicoke, carbon proportion reaches 95%, can be used to produce ferrosilicon and calcium carbide etc.
4. Direct Hydrogenation liquefaction: coal, catalysts and solvents oil is mixed, under High Temperature High Pressure, make coal in destruction of organic material, be converted into low molecule liquid state and gaseous product with hydrogen effect.But the technology of DCL/Direct coal liquefaction is immature, and investment is quite high, and running cost is also quite large.
At present, be directed to incoherence or the weak caking coals such as brown coal, long-flame coal, bottle coal, also lack comprehensively deep processing method of one, to utilize better dross coal or weak caking coal.
CN101643654A discloses the complete processing of a kind of dross coal or weak caking coal, comprises the steps: a) dross coal or weak caking coal to be carried out to middle low-temperature pyrolysis reaction, generates coal gas, semicoke and coal tar; B1) by pressure-variable adsorption, the hydrogen in described coal gas is proposed; B2) described semicoke is sent into coal-gas producer, in coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash, and described synthetic gas comprises carbon monoxide and hydrogen; Or described semicoke is sent into circular fluid bed to generate electricity; B3) described coal tar is carried out to normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and tower, at the bottom of tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running; Carbolic oil carries out carbolic oil extracting and obtains phenols and dephenolize oil; C) by step b3) in lighting end, dephenolize oil and last running, carry out hydrogenation reaction with hydrogen.CN101580728A discloses the complete processing of a kind of dross coal or weak caking coal, comprises the steps: first, under middle low temperature, dross coal or weak caking coal is carried out to middle low-temperature pyrolysis, generates semicoke, coal gas and coal tar; Then respectively these three kinds of destructive distillation products are processed, first, by semicoke by being gasificated into synthetic gas, then synthetic gas is carried out to the synthetic paraffin class hydro carbons of preparing of fischer-tropsch, second, utilize pressure swing adsorption that the hydrogen in coal gas is proposed, the 3rd, coal tar is carried out to fractionation, fractionation obtains oil at the bottom of carbolic oil, overhead oil and tower, carries out again extracting for carbolic oil, obtains phenols and dephenolize oil, heavy oil at the bottom of tower and dephenolize oil are carried out to delayed coking, obtain coking gas, coking naphtha, coker gas oil, wax tailings and coke; Then, utilize the hydrogen of extracting to carry out hydrotreatment to paraffin hydro carbons and coking naphtha, coker gas oil, wax tailings; Finally, the hydrogenation output obtaining is respectively mixed.In such scheme, all relate to the hydrogenation process of coal tar, but hydrogenation process is single, concerning the very poor coal tar of quality, cannot reaches satisfied effect.
CN93107496.7 provides a kind of method of being produced diesel oil by middle coalite tar, i.e. direct chemical refining method is processed the diesel oil distillate of coal tar by the method for removal of impurities-refining-washing-breakdown of emulsion-allotment, and refining goes out to reach the diesel oil of service requirements.CN94112466.5 relates to the method with prodn. of diesel for coal tar oil, and coal tar is main raw material, adds auxiliary material, through mix and blend, catalyzed oxidation-distillation and synthetic three technological processs, can obtain 0-35# diesel oil.CN88105117 has introduced a kind of formula and compound method thereof of fuel reagent replacing diesel, and its product, only as fuel, is not suitable for diesel engine.These methods are all that coal tar is carried out to chemical treatment, poor product quality, and light oil yield is low, does not reach the comprehensive utilization to tar resource.
Hydrogen addition technology is the effective ways that improve coal tar quality, and under hydrogenation catalyst exists, coal tar reacts with hydrogen, removes the impurity in coal tar or further transforms.The hydrocracking of coal tar is the effective means taking coal tar processing as high quality light ends.In general, hydrocracking technology comprises two sections of serial hydrocrackings, one-stage serial hydrocracking and single-stage hydrocracking technology, two-stage hydrocracking first will remove and separate the poisonous material of hydrocracking catalyst under hydrofining condition, then carries out hydrocracking reaction; One-stage serial hydrocracking uses the hydrocracking catalyst of resistance to ammonia, and first raw material first passes through hydrofining reaction district, and the nitrogen organic in raw material is converted into ammonia, and hydrofining reaction product directly enters hydrocracking section without separation and reacts; Single-stage hydrocracking uses the hydrocracking catalyst with resistance to organic nitrogen compound, and raw material directly carries out hydrocracking without hydrofining.
For coal tar raw material, owing to containing more nitrogen, sulphur, oxygen impurities in raw material, these impurity can be converted into ammonia, hydrogen sulfide and water in the time of hydrotreatment, these materials have obvious negative effect to follow-up hydrocracking catalyst, particularly water can make the surface acidity irreversibility of hydrocracking catalyst weaken, and then reactivity worth decline, the work-ing life of catalyzer is shorter, and cannot be by regeneration restorability.Therefore, the hydrocracking of coal tar raw material adopts two-stage method more suitable, and first paragraph is hydrotreatment section, and second segment is hydrocracking section, and the reaction product of hydrotreatment section enters second segment hydrocracking section after imurity-removal.Owing to adopting two-stage hydrocracking technology, therefore, how organic cooperation between two sections, just can reach the net effect such as reduce energy consumption, extending catalyst work-ing life, improve the quality of products, improve the competitive power of production equipment, need to be technique, the aspect such as engineering and catalyzer carries out technological innovation.
In coal tar, contain lighting end (being mainly diesel oil distillate) and last running, for the processing of lighting end, prior art has more suitable processing technology, one stage hydrofining technology, and two-stage hydrogenation modification technology etc. all can obtain the product of suitable quality.But for the processing and utilization of last running, prior art does not have suitable method.In currently available technology, need only and adopt two-stage hydrocracking to process last running, or last running is processed in coking.While adopting two-stage hydrocracking to process last running, topmost problem is to contain in last running the materials such as more condensed-nuclei aromatics, particularly be easy to coking on hydrocracking catalyst surface on hydrogenation catalyst surface, the work-ing life of catalyzer is shorter, even the method by methods such as underpressure distillation, the heaviest cut being cut out at present, still be not enough to ensure the long-term operation of hydroeracking unit, because a transformation efficiency of hydroeracking unit is generally 30%～70% left and right, unconverted last running need to constantly circulate in hydroeracking unit, and the constantly accumulation in working cycle of macromole condensed-nuclei aromatics, cause on the one hand the obstruction of some cyrogenic equipment, have a strong impact on the other hand the work-ing life of hydrocracking catalyst.
CN101307257A discloses a kind of coal tar hydrogenation modification method of two-stage method, coal tar is cut into coal tar lighting end and coal tar heavy fractioning through air distillation and/or underpressure distillation, after coal tar lighting end and optional distillate mix with hydrogen, enter the first hydroconversion reaction zone and Hydrobon catalyst contact reacts, its reaction effluent enters the second hydroconversion reaction zone after intermediate flash tower or high-pressure stripper remove contained gaseous impurities, with catalyst for hydro-upgrading or hydrocracking catalyst contact reacts, the reaction effluent of gained is through cooling, after separation and fractionation, obtain diesel oil distillate and naphtha fraction.The lighting end that has only utilized coal tar of the method, cut point is 300～380 DEG C, and the last running that exceedes diesel oil distillate is all utilized, and the utilization ratio of coal tar is low.
CN101629099A discloses a kind of two-stage method coal tar hydro-conversion method.Coal tar hydro carbons at hydrofining Partial Conversion for the conventional boiling point of institute hydrocarbon-containifirst all lower than the hydrofining reaction effluent of 370 DEG C and be isolated at least one hydrofining diesel oil; At least a portion hydrofining diesel oil is hydro-upgrading reaction effluent and is isolated to hydro-upgrading diesel oil at hydro-upgrading Partial Conversion.The boiling point that the method is only used in coal tar is lower than the cut of 370 DEG C, and coal tar utilization ratio is low.
CN102051222A discloses the high nitrogen high aromatic oil of a kind of two-stage method hydrogenating conversion process, the cold high score oil of a section of the first raw material hydrocarbon 1LL wax oil cut content is lower, and one section of cold high score oil 1LL enters two section of first reaction zone 2R1 and completes diesel oil hydrogenation modification reaction and be converted into two section of first reaction zone reaction effluent 2R1P; When two section of first reaction zone 2R1 passed through in one section of cold high score gas series connection of at least a portion, form the full serial flow of high-pressure section; Further, separate main by treating that the hydrocarbon stream 2FHP that crackene component forms enters the 3rd hydroconversion reaction zone 3R that uses hydrocracking catalyst that 2R1P obtains, the 3rd hydrogenation reaction effluent 3RP mixes with 2R1P or enters reaction zone 2R1 or enter one stage hydrofining reaction zone 1R.The method is also only applicable to carbolineum or coal-tar base intermediate oil two-stage method hydrogenation process, and hydrogenation last running tail oil can only be used for the oil fuel of low value, and coal tar utilization ratio still needs further raising.
CN102031146A discloses a kind of two-stage method high aromatic oil hydrogenating conversion process, one-stage hydrogenation generates oily heavy cracking stock and reacts to reduce second pyrolysis at two sections of two section of first reaction zone 2R1 (high boiling fraction hydrocracking reaction district) by series connection and two sections of Unicracking-JHC reaction zone 2RU (low boiler cut cracking reaction district), and one-stage hydrogenation generates the light cracking stock 1LBO of oil (light wax oil cut and or heavy gas oil cut) introducing reaction zone 2RU; One-stage hydrogenation reaction effluent can separate respectively or combined separation with two sections of section hydrogenation reaction effluents; Secondary hydrogenation can be generated to the heavy cracking stock of oil and introduce 2R1, the light cracking stock of secondary hydrogenation generation oil can be introduced to 2RU and realize circulation cracking.The output that although heavy cracking stock circulation cracking can improve coal tar produces light Fuel, the condensed-nuclei aromatics content of coal tar is high, particularly heavily higher in cracking recycle stock, and can constantly accumulate, and causes catalyst carbon deposit deactivation rate to accelerate.
CN102021028A discloses a kind of two-stage method high aromatic oil hydrogenating conversion process, the one-stage hydrogenation of the first raw material hydrocarbon generates oily last running and reacts to reduce second pyrolysis at two sections of two section of first reaction zone 2R1 (high boiling fraction cracking reaction district) by series connection and two sections of second reaction zone 2RU (diesel modifying reaction zone), and one-stage hydrogenation reaction effluent and two sections of section hydrogenation reaction effluents carry out combined separation; Partial hydrogenation can be generated to oily lighting end 1LBO (diesel oil distillate and or naphtha fraction, be generally heavy gas oil cut) and introduce diesel modifying reaction zone 2RU; Can be between two sections of devices of the independent fractionation of the separating of oil part of hot high score hot high score oil and or one section of hot high score oil of device obtain high boiling fraction and enter cracking and hydrogenation cracking reaction district 2R1 circulation cracking, thereby utilize hot high score hydrogenated oil to be completed to the effect of initial gross separation.The method does not relate to coking heavy distillate utilization ratio yet and improves, and short problem running period that causes because of coking of hydrocracking catalyst.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the technical problem that the present invention solves is, the deep processing method of a kind of dross coal or weak caking coal is provided, this technique is passed through the technique means such as the optimum combination of flow process, in improving coal tar production light-weight fuel oil yield, the work-ing life of extending catalyst, the running period of improving device.
The deep processing method of dross coal of the present invention or weak caking coal comprises the steps:
A) dross coal or weak caking coal are carried out to middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of described middle low-temperature pyrolysis reaction is 450～700 DEG C;
B) described coal tar is adopted with the following method and is processed:
(b1) oil gas that coal tar raw material, delayed coking reaction obtain separates with at least part of step (b4) high-pressure separator the liquid phase obtaining and jointly enters distillation tower, distills out oil at the bottom of naphtha fraction, carbolic oil cut, wax oil cut and tower; Naphtha fraction and hydrogen are mixed into petroleum naphtha hydrogenation refining reaction section, exist and contact with Hydrobon catalyst with under hydrofining condition at hydrogen, carry out hydrofining reaction; The dephenolize oil that carbolic oil cut obtains after dephenolize is mixed into hydrotreatment conversion zone with wax oil cut, exists and contacts with hydrotreating catalyst under hydroprocessing condition at hydrogen, carries out hydrotreatment reaction;
(b2) hydrotreatment conversion zone reaction effluent carries out gas-liquid separation, and the liquid phase of separation enters fractionation plant, and fractionation is lighting end and last running;
(b3) last running that step (b2) obtains enters hydrocracking reaction section at least partly, exists and contacts with hydrocracking catalyst under hydrocracking condition at hydrogen, carries out hydrocracking reaction;
(b4) hydrocracking reaction section reaction effluent enters high-pressure separator, is separated into gas phase and liquid phase, and liquid phase enters the distillation tower of step (b1) at least partly;
(b5) at the bottom of step (b1) is distilled the tower obtaining, oil enters delayed coking unit, and the distillation tower that the oil gas that delayed coking unit obtains enters step (b1) distills processing.
In the inventive method, can also comprise the steps:
C1) by pressure swing absorption process, the hydrogen in described coal gas is separated; The hydrogen obtaining can be for the hydrogenation process of step b).
C2) described semicoke is sent into coal-gas producer, in coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash, and described synthetic gas comprises carbon monoxide and hydrogen; Utilize described synthetic gas to carry out F-T synthesis reaction and produce paraffin class hydro carbons.The coke that delayed coking unit obtains also can enter this coal-gas producer.
In the inventive method step a), dross coal or weak caking coal are one or more in brown coal, long-flame coal and bottle coal.
In the inventive method step (b1), coal tar raw material also can be mixed the raw material in other source simultaneously.Coal tar raw material can be carried out conventional pre-treatment before entering distillation tower, as dehydration, and desalination, the processing such as de-solid impurity.
In the inventive method step (b1), the final boiling point of the naphtha fraction that distillation tower distills out is 150～190 DEG C, is preferably 160～180 DEG C; The initial boiling point of wax oil cut is generally 270～400 DEG C, is preferably 270～350 DEG C, and the final boiling point of wax oil cut is generally 480～700 DEG C, is preferably 530～650 DEG C; Carbolic oil cut is the distillate between naphtha fraction and wax oil cut.
In the inventive method step (b1), the hydrofining condition of naphtha fraction is generally: volume space velocity 0.3～3.5h when 180～380 DEG C of temperature of reaction, pressure 3.0～10.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1.Preferred hydroprocessing condition is: volume space velocity 0.5～2.0h when 200～360 DEG C of temperature of reaction, pressure 4.0～8.0MPa, hydrogen to oil volume ratio 1000:1～2000:1 and liquid
-1.
In the inventive method step (b1), hydroprocessing condition is generally: volume space velocity 0.1～1.5h when 180～435 DEG C of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1.Preferred hydroprocessing condition is: volume space velocity 0.2～0.8h when 200～400 DEG C of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～3000:1 and liquid
-1.
In the inventive method step (b1), hydrofining reaction pressure is preferably lower than hydrotreatment reaction pressure 5～12MPa.Hydrofining reaction section is preferably used hydrogen once by flow process, and hydrofining reaction effluent is after gas-liquid separation, and liquid phase is petroleum naphtha after hydrogenation, and gas phase is the hydrogen make-up for hydrotreatment conversion zone through supercharging.
In the inventive method step (b1), Hydrobon catalyst and hydrotreating catalyst are conventional Hydrobon catalyst and hydrotreating catalyst.Hydrobon catalyst and hydrotreating catalyst be generally taking aluminum oxide as carrier, and taking one or more in Mo, W, Co and Ni as active ingredient, catalyzer carried out routine and vulcanizes before using, and made active ingredient be converted into sulphided state.In catalyzer, can contain suitable auxiliary agent, as one or more in Si, P, F, Ti, Zr, B etc.Active component content in oxide weight in catalyzer is generally 5%～55%, is preferably 15%～35%.The pore volume of catalyzer is generally 0.3～0.6mL/g, and specific surface area is generally 80～350m
2/ g.The catalyzer of hydrofining section and hydrotreatment section can use one, also can use two or more.Reaction mass can contact with protective material before hydrofining or hydrotreatment, and protective material consumption is generally 10%～100% of Hydrobon catalyst or hydrotreating catalyst volume.Reaction conditions when reaction mass contacts with protective material as temperature, pressure, hydrogen to oil volume ratio etc. can be basic identical with hydrofining or hydroprocessing condition; also can be different, preferable reaction temperature can be lower than 10～100 DEG C of hydrofining or hydrotreating reactors.Protectant active ingredient (one or more in Mo, W, Co and Ni) is generally 0～20% in the content of oxide weight, is preferably 1%～15%, and pore volume is generally 0.4～1.5mL/g, and specific surface area is generally 20～200m
2/ g.Protective material can use one, preferably arranges 2～5 kinds, and every kind of protectant consumption is at least 15% of protective material cumulative volume consumption.Reduce successively by the pore volume of Flow of Goods and Materials direction protection agent, active component content increases successively, to improve integrated protection effect.Protective material can be arranged on separately in a reactor, also can all or part ofly be arranged in same reactor with hydrotreating catalyst (or Hydrobon catalyst).Protective material described in the application, taking aluminum oxide as carrier, has appropriate active ingredient, has removing impurities matter as demetalization impurity function, and to protect follow-up hydrogenation to process catalyzer, therefore protectant concept has comprised Hydrodemetalation catalyst in prior art.
In the inventive method step (b2), the conventional separation column that fractionation plant comprises, the cut-point of lighting end and last running is generally within the scope of 170～360 DEG C, preferably within the scope of 200～300 DEG C.Lighting end is mainly diesel oil distillate and a small amount of naphtha fraction, and hydrocracked, treated is carried out in last running.
In the inventive method step (b3), hydrocracking reaction condition is generally: volume space velocity 0.1～1.2h when 350～445 DEG C of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 500:1～5000:1 and liquid
-1.The most preferred reaction conditions of hydrocracking is as follows: volume space velocity 0.2～0.8h when 375～425 DEG C of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～2000:1 and liquid
-1.
In the inventive method step (b3), hydrocracking catalyst can adopt the hydrocracking catalyst of this area routine, and hydrocracking catalyst generally comprises cracking component and hydrogenation component, and other component such as aluminum oxide, auxiliary agent.Wherein cracking component is at least one in molecular sieve and amorphous aluminum silicide, the weight content of cracking component in hydrocracking catalyst is generally 20%～70%, be preferably 30%～60%, molecular sieve is generally Hydrogen Y molecular sieve, modification Hydrogen Y molecular sieve, in amorphous aluminum silicide, the weight content of silicon-dioxide is generally 15%～55%.Hydrogenation component is one or more in Mo, W, Co and Ni, and the content in oxide weight in catalyzer is generally 15%～40%, is preferably 25%～35%.The pore volume of hydrocracking catalyst is generally 0.3～0.5mL/g, and specific surface area is generally 200～400m
2/ g.Hydrocracking catalyst carries out conventional sulfidizing before use, makes active ingredient be converted into sulphided state.In the inventive method, in hydrotreatment and hydrocracking process, can supplement as required appropriate sulphur or sulfocompound, in reaction process, process in the good sulphided state of activity to maintain hydrotreating catalyst and hydrocracking catalyst.
In step of the present invention (b3), in reaction mass, preferably supplement off and on appropriate NH
3, supplement NH
3in process, NH
3concentration in reaction system gaseous phase materials is 100～2000 μ g/g, is preferably 300～800 μ g/g(and mends NH
3method is: supplement liquefied ammonia at reactor inlet; Analytical procedure is: reactor outlet gaseous phase materials is analyzed).Supplement NH
3can every running preferably within 5th～30, carry out once for 1st～100, carry out 1～12 hour at every turn.Can reduce like this hydrocracking catalyst carbon deposit, increase the service life.Supplement NH
3process in preferably increase the hydrogen to oil volume ratio of operation, for example, can be than normal running time, improve 200～1000.
In step of the present invention (b4), the isolated liquid phase of high-pressure separator also can partly enter the fractionation plant in (b2).High-pressure separator adopts cold high pressure separator, the service temperature of cold high pressure separator is generally 40～80 DEG C, and working pressure identical with hydrocracking reactor working pressure (ignoring the pressure-losses) adopts cold high pressure separator can greatly reduce number of devices, simplify flow process, reduce investment.
In the inventive method step (b5), 450 DEG C～550 DEG C of delayed coking reaction temperature, reaction pressure 0.1MPa～0.5MPa; 485 DEG C～535 DEG C of preferable reaction temperature, preferred reaction pressure 0.15MPa～0.35MPa.Delayed coking reaction product and coking raw material adopt a set of distillation column system, and distillation tower is close with working method with conventional delayed coking product distillation tower structure, is content well known to those skilled in the art.
In the inventive method, hydrotreatment section and hydrocracking section can arrange respectively recycle hydrogen system, also can adopt a set of recycle hydrogen system.While adopting a set of recycle hydrogen system, the gas phase after the gas-liquid separation of hydrotreatment section reaction effluent enters hydrocracking section after imurity-removal, and the gas phase after the gas-liquid separation of hydrocracking section reaction effluent is circulated to hydrotreatment section and recycles.
In the inventive method step (b1), the dephenolize of carbolic oil cut all can adopt this area ordinary method.For example phenol removal adopts soda acid method for extracting, specifically can adopt conventional coal tar carbolic oil refining plant, and carbolic oil cut enters extraction tower, adds alkaline solution in extraction tower, and the phenates extracting is through steaming stripping oil, sulfuric acid or CO
2after decomposing, obtain phenol products, obtain dephenolize oil after extracting phenol products.
In the inventive method step (c1), pressure-variable adsorption recover hydrogen is this area ordinary method, for example specific as follows:
Pressure-variable adsorption or be called PSA Technology, it is the principle of the physical adsorption balance on solid adsorbent based on gas, taking sorbent material under different pressures condition to mixture in different components equilibrium adsorption capacity difference as basis, under high pressure adsorb, under low pressure desorption, thus realize the chemical circulation operating process of mixture separation.The typical process of the pressure-variable adsorption of coal gas is, coal gas is raised to the required pressure of absorption through gas compressor by pressure, make the temperature of coal gas reach the desired temperature of absorption through cooling system again, heavy hydrocarbon impurity (as tar, benzene and naphthalene etc.) in coal gas will be adsorbed in preadsorption system, the coal gas of rough purification carries out impurity absorption through adsorption system again, purer hydrogen out from adsorber.
Preferably, in pressure-swing adsorption process, the adsorption bed of utilization comprises aluminum oxide, silica gel, gac, zeolite molecular sieve and absorbent for carbon monooxide, and working pressure is 0.8MPa～2.8MPa.
Preferably, before hydrogen is suggested, described coal gas is at high temperature contacted with water.In coal gas, also contain carbon monoxide, for carbon monoxide, can depending on the required hydrogen of hydrogenation in subsequent technique consumption number or other install required amounts of hydrogen judge its whether adopt in change technology it react to generation hydrogen again with water, together with the hydrogen that the hydrogen becoming in carbonic oxide can produce with the dry distillation of coal, adopt pressure swing adsorption to propose, for the feed hydrogen of hydrogenation reaction.Middle change technology is exactly to make carbon monoxide react the technology of producing hydrogen with water, and this is well known to those skilled in the art, and repeats no more here.
Coal gas, before carrying out pressure-variable adsorption, can suitably purify.
In the inventive method step (c2), semicoke belongs to this area routine techniques for the production of coal gas, and for example detailed process is as follows:
First,, in coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash.Synthetic gas comprises carbon monoxide and hydrogen.Coal-gas producer can be fixed-bed type, fluidized bed-type and fluidized bed type, preferably uses fluidized bed type coal-gas producer.Preferably, the reaction pressure of fluidized bed type coal-gas producer is 0.1MPa～4.5MPa, and temperature of reaction is 650 DEG C～1100 DEG C, and gas-solid volume ratio is 3～8; More preferably, the reaction pressure of fluidized bed type coal-gas producer is 0.1MPa～3.5MPa, and temperature of reaction is 700 DEG C～1000 DEG C, and gas-solid volume ratio is 4～8.In this step, the volume ratio of oxygen and water vapour is 3～9.
Then, synthetic gas is prepared paraffin class hydro carbons by F-T synthesis reaction.F-T synthesis reaction is method well known to those skilled in the art.Concrete next under suitable reaction conditions, adjust the volume ratio of hydrogen and carbon monoxide, under high-selectivity catalyst effect, adjust the distribution of reaction product, its primitive reaction is that carbon monoxide and hydrogen addition generate hydro carbons.The 6th chapter on " the Coal Chemical Industry basis " that specifically can write referring to people such as Li Yulin, Chemical Industry Press publishes, August in 2008 the 1st edition etc.
Be directed to the complete processing of dross coal provided by the present invention or weak caking coal, preferably, the F-T synthesis reaction device that F-T synthesis reaction adopts is slurry state bed formula F-T synthesis reaction device; More preferably, the temperature of reaction of F-T synthesis reaction is 120 DEG C～450 DEG C, and reaction pressure is 0.05MPa～10MPa, and synthetic gas is 100h for the volume space velocity of reactor volume
-1～5000h
-1; Most preferably, the temperature of reaction of F-T synthesis reaction is 150 DEG C～100 DEG C, and reaction pressure is 0.1MPa～10MPa, and synthetic gas volume air speed is 200h
-1～5000h
-1.Utilize above-mentioned technique, not only well solve the liquefaction of semicoke, the more important thing is that the cetane value of the oil product of producing after the synthetic paraffin class hydro carbons of producing of fischer-tropsch is by hydrotreatment is generally in 60～70 left and right, can further promote the cetane value that coal tar hydrogenating reaction obtains diesel product, produce the clean diesel of high grade.The synthetic paraffin class of producing of fischer-tropsch can carry out hydro-upgrading with coal tar simultaneously, also can adopt independent hydrogenation unit to process.
Compared with prior art, tool of the present invention has the following advantages:
1. the fractionation of the fractionation of coal tar raw material, pyrogenic reaction oil gas and hydrocracking are generated to oily fractionation and become one, simplified flow process, facility investment is low, takes full advantage of the heat of pyrogenic reaction high-temperature oil gas, effectively reduces energy consumption.Coking naphtha cut and hydrocracking naphtha fraction do not enter the hydrotreatment conversion zone of last running, adopt independent hydrofining reaction section to process, be conducive to reduce facility investment (hydrofining section required reaction pressure lower), improved the reaction depth (having improved the hydrogen dividing potential drop of hydrotreatment reaction process) of heavy fractioning hydrogenation processing.The product of hydrotreatment section carries out fractionation processing, and the last running obtaining enters hydrocracking section.Can avoid like this lighting end that too much scission reaction occurs, object product yield is high, and the product yields such as the dry gas of low value are low, improved whole economic efficiency.
2. the liquid phase circulation that hydrocracking reaction generates to a point distillation tower for coal tar raw material and coking oil gas distills processing jointly, this flow process is different from hydrocracking reaction effluent and all enters hydrotreating reactor, and the liquid phase that is also different from hydrocracking reaction effluent all enters fractionating system and carries out fractionation processing.This flow process tool has the following advantages: what in hydrocracking reaction process, meeting produced is easy to oil at the bottom of the macromole condensed-nuclei aromatics of catalyst active center's coking enters tower in still-process, and then adopt coker to process, avoid macromole condensed-nuclei aromatics to enter hydrogenation unit accelerator activator carbon deposit.Simultaneously, also avoid the light constituent in hydrocracking reaction effluent to enter hydrotreating reactor, greatly improve the hydrogen dividing potential drop in hydrotreating reactor (if light constituent enters hydrotreating reactor, light constituent can be in gas phase state, reduce the hydrogen concentration in reaction system, reduced hydrogen dividing potential drop), under the constant condition of stagnation pressure, hydrogen dividing potential drop improves the hydrogenation reaction being conducive in hydrotreating reactor, the particularly hydrogenation saturated reaction of condensed-nuclei aromatics, and condensed-nuclei aromatics hydrogenation saturated after, in follow-up hydrocracking reactor, be easy to carry out hydrocracking reaction, reduce coking reaction, extend the work-ing life of hydrocracking catalyst.Simultaneously, hydrocracking high pressure hot separator liquid phase enters hydrotreating reactor, can dilute coal tar raw material, reduces the wherein probability of the polymerization coking such as two rare hydrocarbon, relax the operational condition of hydrotreating reactor, be conducive to extend the work-ing life of hydrotreating catalyst.And isocrackate adopts the operating method of high pressure hot separator, also can effectively avoid macromole condensed-nuclei aromatics to separate out the problem of occluding device.
3. oil gas and the isocrackate that delayed coking produces is jointly together separating in distillation tower, the naphtha fraction obtaining comprises coking naphtha and hydrocracking petroleum naphtha, both mixed hydrogenations are refining, avoided problem in independent coking naphtha unifining process, the problem includes: device short problem running period that easy coking causes.
4. in hydrocracking reactor operating process, preferably supplement off and on appropriate NH
3.This operating method can effectively reduce hydrocracking catalyst carbon deposit, extends the work-ing life of hydrocracking catalyst.Find after deliberation, the carbon deposit major cause of hydrocracking catalyst is that condensed-nuclei aromatics is wherein adsorbed on acidity of catalyst center, constantly assembles polymerization, under hot conditions, and the hydrogenation that is not able to do in time, and there is polymerization coking reaction.In reaction process, special in the operating method of unconverted circulation, the macromole condensed-nuclei aromatics in recycle stock not section accumulation increases (under hot conditions, generating), and therefore, along with the carrying out of reaction, hydrocracking catalyst has the trend of inactivation quickening.The present invention finds by research, in coal tar hydrogenating reaction process, owing to adopting two sections of flow processs, enters impurity in hydrocracking reactor less, by the appropriate NH of regular replenishment
3, NH
3can on the acid sites of hydrocracking catalyst, form competitive adsorption with macromole condensed-nuclei aromatics, avoid macromole condensed-nuclei aromatics long-time absorption accumulation and then coking on acid sites.NH
3introducing formed competitive adsorption, can make to adsorb the macromole condensed-nuclei aromatics desorption of receiving in large acidity enters in the oil phase of reaction system, and discharge hydrocracking reactor and enter hydrotreating reactor, catalyst performance in hydrotreating reactor and reaction conditions are more suitable for the hydrogenation saturated reaction of macromole condensed-nuclei aromatics, macromolecular substance after hydrogenation is saturated is easy to occur hydrocracking reaction, and coking reaction reduces greatly.Therefore, the inventive method can effectively reduce the coking tendency of hydrocracking catalyst, extending catalyst work-ing life.At supplementary NH
3process in, suitably strengthen hydrogen-oil ratio and can effectively improve the desorption of macromole condensed-nuclei aromatics, further improve treatment effect.At supplementary NH
3process in, the cracking performance of hydrocracking catalyst slightly declines, per pass conversion only declines 1～2 percentage point, does not substantially affect normal running, and the selectivity of intermediate oil increases, the total economy of body is unaffected, stops supplementing NH
3after, reactivity worth is quick-recovery soon.
5. compared with prior art, it is synthetic again for the production of paraffin class hydrocarbon that the synthetic gas after char Gasification carries out fischer-tropsch to the deep processing method of dross coal provided by the present invention or weak caking coal, and for final production oil product.In addition, the hydrogen arriving in pressure-variable adsorption, for hydrogenation reaction, has also improved the utilization ratio of coal gas.
Brief description of the drawings
Fig. 1 is a kind of concrete technology schematic flow sheet of the present invention.Wherein: 1-coal tar raw material, 2-hydrotreating reactor, 3-hydrotreatment reaction effluent gas-liquid separator, 4-separation column, 5-hydrocracking reactor, 6-recycle hydrogen de impurity device, 7-hydrotreated naphtha cut, 8-diesel oil distillate, 9-high-pressure separator, 20-hydrogen make-up, 21-distillation tower, 22-delayed coking unit, 23-hydrofining reactor, 24-hydrofining reaction product gas-liquid separator, 25-dephenolize device, 26-mixing naphtha fraction, 27-wax oil cut, 28-delayed coking reaction oil gas, 29-hydrofining petroleum naphtha, 30-dross coal or weak caking coal, 31-dry distillation of coal device, 32-dry distillation gas pressure-variable adsorption separating hydrogen gas device, 33-semicoke preparing synthetic gas device, the fischer-tropsch synthesizer of 34-synthetic gas hydrocarbon processed.
Embodiment
Further illustrate method of the present invention and effect below by specific embodiment.As shown in Figure 1, low-temperature pyrolysis in dross coal or weak caking coal process, obtains dry distillation gas, coal tar and semicoke; Dry distillation gas adopts pressure swing absorption process by Hydrogen Separation wherein, and the hydrogen obtaining is for adding the naphtha fraction hydrofining reactor of hydrogen partial; Semicoke enters gazogene and obtains the synthetic gas as leading taking carbon monoxide and hydrogen, and synthetic gas can adopt Fischer-Tropsch synthesizer to obtain synthin.A kind of concrete technology flow process of coal tar hydrogenating part of the present invention is: coal tar raw material and delayed coking oil gas and hydrocracking generate oil and jointly enter distillation tower 21, obtain mixing naphtha fraction 26(through distillation and comprise coking naphtha cut, hydrocracking naphtha fraction, and naphtha fraction in a small amount of coal tar), carbolic oil cut, oil at the bottom of wax oil cut and tower, at the bottom of tower, oil enters delayed coking unit 22.Mixing naphtha fraction 26 and enter petroleum naphtha hydrogenation refining reaction section, reclaim hydrofining petroleum naphtha 29 after reaction, is good catalytic reforming raw material; Gas phase after further increase for hydrotreatment conversion zone.Carbolic oil cut jointly carries out hydrotreatment with wax oil cut and reacts after the dephenolize of dephenolize device, carry out the reactions such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation, rare hydrocarbon be saturated, reaction effluent carries out fractionation, obtains diesel oil distillate 8 after hydrogenation, and last running enters hydrocracking reaction district.Hydrotreatment reaction effluent after gas-liquid separation, gas phase after imurity-removal for hydrocracking reaction.Hydrocracking reaction effluent is separated into liquid and gas in high-pressure separator 9, and liquid phase circulation returns distillation tower 21, after gas phase treatment, recycles.
Embodiment 1
Nanning brown coal are sent in fluidized bed dry distillation reactor and carried out dry distillation reactor, pressure 0.1MPa, 500 DEG C of service temperatures, generate coal gas, coal tar and semicoke.Coal tar oil properties is in table 1.After gas purification, enter pressure-swing absorption apparatus, by the adsorption bed being formed by zeolite molecular sieve etc., working pressure is 2MPa, hydrogen is wherein proposed, and carbon monoxide component wherein, also in adopting, change technology react it to have generated hydrogen with water again, adopts pressure swing adsorption proposition charging for coal tar hydrogenating unit together with the hydrogen producing with the dry distillation of coal.Semicoke, sends into fluidized bed coal gas generator, and oxygen, water vapour reaction produce synthetic gas and coal ash.When char Gasification, semicoke reacts with oxygen, water vapour (volume ratio of water vapour, oxygen is 5:l) and produces synthetic gas (carbon monoxide and hydrogen) and coal ash; Coal-gas producer reaction pressure 0.13MPa, 900 DEG C of temperature of reaction, gas-solid ratio 5:1 (v/v), wherein the volume ratio 4:1 of water vapor, oxygen.The synthetic gas that gasification produces enters F-T synthesis reaction device, reaction pressure 0.6MPa, and 180 DEG C of temperature of reaction, synthetic gas air speed is 4000h
-1, generating paraffin class hydrocarbon, paraffin hydro carbons can enter the hydrocracking reaction section (processing that the present embodiment is unmixed) in apparatus of the present invention.
Coal tar carries out processing treatment by flow process shown in Fig. 1 after de-mechanical impurity and water.
Coal tar raw material and delayed coking oil gas and hydrocracking liquid product enter separation column, fractionate out naphtha fraction (C5～180 DEG C), carbolic oil cut (180～290 DEG C), wax oil cut (290～550 DEG C).Naphtha fraction carries out hydrofining, and carbolic oil cut carries out phenol removal, and dephenolize oil and wax oil cut carry out hydrotreatment, obtain diesel oil distillate and heavy oil fraction (by 325 DEG C of cuttings) after hydrotreatment, and heavy oil fraction carries out hydrocracked, treated.At the bottom of tower, oil enters delayed coking unit.
The service temperature of delayed coking unit is 510 DEG C, and pressure is 0.15MPa.Hydrorefined temperature of reaction device temperature in is 280 DEG C, and reaction temperature rising is 80 DEG C, volume space velocity 1.5h when reaction pressure is 6.0MPa, hydrogen to oil volume ratio 800:1 and liquid
-1; Volume space velocity 0.64h when the temperature of reaction of hydrotreatment is 350 DEG C, pressure 15.1MPa, hydrogen to oil volume ratio 1000:1 and liquid
-1; Volume space velocity 0.3h when 375 DEG C of the temperature of reaction of hydrocracking, pressure 15.9MPa, hydrogen to oil volume ratio 1200:1 and liquid
-1.Hydrotreating catalyst and Hydrobon catalyst are identical hydrogenation catalyst, and this hydrogenation catalyst is with alumina supporter, and molybdenum oxide weight content is 15%, and Tungsten oxide 99.999 weight content is 12%, and nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume is 0.35ml/g.Hydrocracking catalyst is conventional hydrocracking catalyst, (silica/alumina molecular ratio is as 12 taking Y zeolite for catalyzer, structure cell is often for 0.2426nm) and amorphous aluminum silicide (silica weight content is 27%, infrared acidity is 0.4mmol/g) be cracking component, Y zeolite weight content is 15%, amorphous aluminum silicide weight content is 35%, Tungsten oxide 99.999 weight content is 28%, nickel oxide weight content is 8%, and surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume is 0.42ml/g.Hydrotreating catalyst and hydrocracking catalyst carry out conventional prevulcanized processing before use.Turn round after 3000 hours, maintain identical transformation efficiency (it is 55% control that transformation efficiency is less than 325 DEG C of distillate weight yields by hydrocracking reactor outlet, lower same) and need 8 DEG C of temperature raisings.The main products quality of main products quality after in Table 3(coal tar hydrogenating, containing the synthetic paraffinic hydrocarbon of fischer-tropsch).
Table 1 coal tar main character
Embodiment 2
Yilan coal is sent in middle fluidized bed dry distillation reactor and carried out dry distillation reactor, pressure 0.12MPa, 600 DEG C of service temperatures, generate coal gas, coal tar and semicoke.Coal tar oil properties is in table 2.Dry distillation gas enters pressure-swing absorption apparatus after purifying, by the adsorption bed being formed by silica gel etc., working pressure is 2.45MPa, hydrogen is wherein proposed, and carbon monoxide component wherein, also in adopting, change technology react it to have generated hydrogen with water again, adopts pressure swing adsorption proposition charging for coal tar hydrogenating unit together with the hydrogen producing with the dry distillation of coal.Semicoke, sends into fluidized bed coal gas generator, and oxygen, water vapour reaction produce synthetic gas and coal ash.When char Gasification, semicoke reacts with oxygen, water vapour (volume ratio of water vapour, oxygen is 3:l) and produces synthetic gas (carbon monoxide and hydrogen) and coal ash; Coal-gas producer reaction pressure 3MPa, 750 DEG C of temperature of reaction, gas-solid ratio 6:1 (v/v), wherein the volume ratio 3:1 of water vapor, oxygen.The synthetic gas that gasification produces enters F-T synthesis reaction device, reaction pressure 7.5MPa, and 300 DEG C of temperature of reaction, synthetic gas air speed is 300h
-1, generate paraffin class hydrocarbon.
The hydrogenation technique of coal tar is identical with embodiment 1.
Table 2 destructive distillation coal tar main character
Embodiment 3
With embodiment 2, hydrotreatment section temperature of reaction is 350 DEG C, before hydrotreatment section, uses hydrogenation protecting agent to carry out pre-treatment; hydrogenation protecting agent is conventional hydrogenation protecting agent, taking aluminum oxide as carrier, containing molybdenum oxide 6%; cobalt oxide 1%, pore volume is 0.82mL/g, specific surface area is 128M
2/ g.The treatment condition of hydrogenation protecting agent are temperature of reaction volume space velocity 1.2h while being 310 DEG C, pressure 15.1MPa, hydrogen to oil volume ratio 1200:1 and liquid
-1.Other is identical with embodiment 2.
Embodiment 4
Press the method for embodiment 3, scheme one: every running 6 days, hydrocracking reactor supplements 2 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 300 μ g/g, after 1500 hours, maintains identical transformation efficiency and needs 1 DEG C of temperature raising.Turn round after 3000 hours, maintain identical transformation efficiency and need 1 DEG C of temperature raising again.Scheme two: every running 30 days, hydrocracking reactor supplements 8 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 800 μ g/g, and the hydrogen to oil volume ratio that increases hydrocracking reactor when mending ammonia is to 2200:1, after 1500 hours, maintain identical transformation efficiency and need 2 DEG C of temperature raisings.Turn round after 3000 hours, maintain identical transformation efficiency and need 1 DEG C of temperature raising again.
Comparative example 1
Press the method for embodiment 1, hydrocracking reaction effluent does not enter water distilling apparatus, and all enters hydrotreating reactor.Turn round after 3000 hours, maintain identical transformation efficiency and need 25 DEG C of temperature raisings.
Comparative example 2
Press the method for embodiment 4, hydrocracking reactor is not mended ammonia operation, turns round after 1500 hours, and while maintaining identical transformation efficiency, temperature of reaction need promote 5 DEG C.Turn round after 3000 hours, maintain identical transformation efficiency and need 4 DEG C of temperature raisings again.
Table 3 the inventive method main products character
| Product main character | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4* |
| Petroleum naphtha | ||||
| Nitrogen content, μ gg -1 | <0.5 | <0.5 | <0.5 | <0.5 |
| Sulphur content, μ gg -1 | <0.5 | <0.5 | <0.5 | <0.5 |
| Virtue is dived, % | 90.3 | 90.7 | 90.8 | 91.4 |
| Diesel oil | ||||
| Sulphur content, μ gg -1 | <5 | <5 | <5 | <5 |
| Nitrogen content, μ gg -1 | <1.0 | <1.0 | <1.0 | <1.0 |
| Cetane value | 40.1 | 44.6 | 44.7 | 44.6 |
* result after turning round 3000 hours by scheme one.
Claims (24)
1. a deep processing method for dross coal or weak caking coal, is characterized in that comprising the steps:
A) dross coal or weak caking coal are carried out to middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of described middle low-temperature pyrolysis reaction is 450～700 DEG C;
B) described coal tar is adopted with the following method and is processed:
(b1) oil gas that coal tar raw material, delayed coking reaction obtain separates with at least part of step (b4) high-pressure separator the liquid phase obtaining and jointly enters distillation tower, distills out oil at the bottom of naphtha fraction, carbolic oil cut, wax oil cut and tower; Naphtha fraction and hydrogen are mixed into petroleum naphtha hydrogenation refining reaction section, exist and contact with Hydrobon catalyst with under hydrofining condition at hydrogen, carry out hydrofining reaction; The dephenolize oil that carbolic oil cut obtains after dephenolize is mixed into hydrotreatment conversion zone with wax oil cut, exists and contacts with hydrotreating catalyst under hydroprocessing condition at hydrogen, carries out hydrotreatment reaction;
(b2) hydrotreatment conversion zone reaction effluent carries out gas-liquid separation, and the liquid phase of separation enters fractionation plant, and fractionation is lighting end and last running;
(b3) last running that step (b2) obtains enters hydrocracking reaction section at least partly, exists and contacts with hydrocracking catalyst under hydrocracking condition at hydrogen, carries out hydrocracking reaction;
(b4) hydrocracking reaction section reaction effluent enters high-pressure separator, is separated into gas phase and liquid phase, and liquid phase enters the distillation tower of step (b1) at least partly;
(b5) at the bottom of step (b1) is distilled the tower obtaining, oil enters delayed coking unit, and the distillation tower that the oil gas that delayed coking unit obtains enters step (b1) distills processing.
2. method according to claim 1, characterized by further comprising following steps:
C1) by pressure swing absorption process, the hydrogen in described coal gas is separated; The hydrogen obtaining is for step hydrogenation process b).
3. method according to claim 1 and 2, characterized by further comprising following steps:
C2) described semicoke is sent into coal-gas producer, in coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash, and described synthetic gas comprises carbon monoxide and hydrogen; Utilize described synthetic gas to carry out F-T synthesis reaction and produce paraffin class hydro carbons.
4. method according to claim 1, is characterized in that: the final boiling point of the naphtha fraction that in step (b1), distillation tower distills out is 150～190 DEG C; The initial boiling point of wax oil cut is 270～400 DEG C, and the final boiling point of wax oil cut is 480～700 DEG C; Carbolic oil cut is the distillate between naphtha fraction and wax oil cut.
5. method according to claim 4, is characterized in that: the final boiling point of the naphtha fraction that in step (b1), distillation tower distills out is 160～180 DEG C.
6. method according to claim 4, is characterized in that: the initial boiling point of the wax oil cut that in step (b1), distillation tower distills out is 270～350 DEG C, and the final boiling point of wax oil cut is 530～650 DEG C.
7. method according to claim 1, it is characterized in that: in step (b1), the hydrofining condition of naphtha fraction is: volume space velocity 0.3～3.5h when 180～380 DEG C of temperature of reaction, pressure 3.0～10.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1;
Hydroprocessing condition is in step (b1): volume space velocity 0.1～1.5h when 180～435 DEG C of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1;
Hydrocracking reaction condition is in step (b3): volume space velocity 0.1～1.2h when 350～445 DEG C of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 500:1～5000:1 and liquid
-1;
In step (b5), delayed coking reaction temperature is 450 DEG C～550 DEG C, and reaction pressure is 0.1MPa～0.5MPa.
8. method according to claim 7, it is characterized in that: in step (b1), the hydrofining condition of naphtha fraction is: volume space velocity 0.5～2.0h when 200～360 DEG C of temperature of reaction, pressure 4.0～8.0MPa, hydrogen to oil volume ratio 1000:1～2000:1 and liquid
-1.
9. method according to claim 7, is characterized in that: hydroprocessing condition is in step (b1): volume space velocity 0.2～0.8h when 200～400 DEG C of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～3000:1 and liquid
-1.
10. method according to claim 7, is characterized in that: hydrocracking reaction condition is in step (b3): volume space velocity 0.2～0.8h when 375～425 DEG C of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～2000:5 and liquid
-1.
11. methods according to claim 7, is characterized in that: in step (b5), delayed coking reaction temperature is 485 DEG C～535 DEG C.
12. methods according to claim 7, is characterized in that: in step (b5), delayed coking reaction pressure is 0.15MPa～0.35MPa.
13. methods according to claim 1, is characterized in that: in step (b1), hydrofining reaction pressure is lower than hydrotreatment reaction pressure 5～12MPa; Hydrofining reaction section adopts hydrogen once by flow process, and hydrofining reaction effluent is after gas-liquid separation, and liquid phase is petroleum naphtha after hydrogenation, and gas phase is the hydrogen make-up for hydrotreatment conversion zone through supercharging.
14. methods according to claim 1, is characterized in that: in step (b1), Hydrobon catalyst and hydrotreating catalyst are conventional Hydrobon catalyst and hydrotreating catalyst; Hydrobon catalyst and hydrotreating catalyst be taking aluminum oxide as carrier, and taking one or more in Mo, W, Co and Ni as active ingredient, catalyzer carried out routine and vulcanizes before using, and made active ingredient be converted into sulphided state; In catalyzer taking the active component content of oxide weight as 5%～55%;
In step (b3), hydrocracking catalyst adopts the hydrocracking catalyst of this area routine, hydrocracking catalyst comprises cracking component and hydrogenation component, wherein cracking component is at least one in molecular sieve and amorphous aluminum silicide, and the weight content of cracking component in hydrocracking catalyst is 20%～70%; Hydrogenation component is one or more in Mo, W, Co and Ni, and the content taking oxide weight in catalyzer is 15%～40%; Hydrocracking catalyst carries out conventional sulfidizing before use, makes active ingredient be converted into sulphided state.
15. methods according to claim 14, is characterized in that: in step (b1), in described catalyzer taking the active component content of oxide weight as 15%～35%.
16. methods according to claim 14, is characterized in that: step (b3), in hydrocracking catalyst, the weight content of cracking component in hydrocracking catalyst is 30%～60%.
17. methods according to claim 14, is characterized in that: step (b3), in hydrocracking catalyst, taking oxide weight, the content in catalyzer is 25%～35% to hydrogenation component.
18. according to the method described in claim 1 or 14; it is characterized in that: in step (b1); reaction mass contacted with protective material before hydrofining or hydrotreatment, and protective material consumption is 10%～100% of Hydrobon catalyst or hydrotreating catalyst volume.
19. methods according to claim 1, is characterized in that: in step (b2), and the conventional separation column that fractionation plant comprises, the cut-point of lighting end and last running is within the scope of 170～360 DEG C.
Method described in 20. claims 19, is characterized in that: in step (b2), and the conventional separation column that fractionation plant comprises, the cut-point of lighting end and last running is within the scope of 200～300 DEG C.
21. methods according to claim 1, is characterized in that: in step (b3), supplement to reaction mass discontinuous appropriate NH
3, supplement NH
3in process, NH
3concentration in reaction system gaseous phase materials is 100～2000 μ g/g; Supplement NH
3adopt every running to carry out once for 1st～100, carry out 1～12 hour at every turn.
22. methods according to claim 21, is characterized in that: in step (b3), and the NH supplementing to reaction mass discontinuous
3concentration in reaction system gaseous phase materials is 300～800 μ g/g.
23. methods according to claim 21, is characterized in that: in step (b3), and supplementary NH
3adopt every running to carry out once for 5th～30.
24. methods according to claim 21, is characterized in that: in step (b3), supplement NH
3process in hydrogen to oil volume ratio improve 200～1000 during than normal running.
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