CN102816596A - 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 technology, 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
World's crude resources short extremely urgent, and distributed pole is unbalanced, and the storage capacity of coal is very abundant, therefore uses coal to produce the approach that the vehicle fuel oil article are a kind of necessity.Major technique by coal system oil comprises the direct liquefaction of coal and the indirect liquefaction of coal etc., but these technical costss are high, technical sophistication.A kind of in addition is the technology of producing coke, can be when producing coke, and by-product coal tar, this is the method that extensively adopts at present.
Dross coal or weak caking coal comprise brown coal, long-flame coal and bottle coal etc.Brown coal are the minimum coals of degree of coalification; 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; The raw material that is used as fuel, gasification also can be used to extract montanin wax and humic acid more, makes sulphonated coal or gac.The volatile content of long-flame coal is also very high, does not have or have only very little cohesiveness, and easy firing has very long flame during burning, so the long-flame coal of gaining the name.Long-flame coal can also can be used as civilian and power fuel as the raw material of gasification.The 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 big, and longitudinal crack is many, and is anti-broken relatively poor with wear resistance.So bottle coal can only be used as coal-blending coking, also can be used to make coal gas, produce nitrogenous fertilizer or power fuel.
In incoherences such as brown coal, long-flame coal and bottle coal or the weak caking coal, all contain abundant organic matter, when middle low-temperature pyrolysis,, also can generate coal gas and coal tar except producing the semicoke.In China, incoherence 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 China's rapid economy development, demands for 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 the abundant relatively country of coal resources, 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 satisfy the needs of national economy high speed development far away.Therefore; For guaranteeing the Sustainable development of Chinese national economy, optimize China's energy structure, reduce interdependency to petroleum import; Make full use of the coal resources advantage of China's abundant; Greatly develop the Coal Chemical Industry new high-tech industry,, become the inevitable choice of China's energy strategy with Coal Chemical Industry products substitution petrochemicals.
The industrialization technology that has incoherences such as utilizing brown coal, long-flame coal, bottle coal or weak caking coal now 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 receives the restriction of the type of furnace, coal, moisture, granularity, can not implement in full.
2. coking: promptly secluding air heats coal, and organic the rising with temperature is decomposed gradually in the coal, and wherein volatile matter is overflowed with gaseous state or vapor state, become coke-oven gas and coal tar, and the non-volatile solids residue is coke.But incoherences such as brown coal, long-flame coal, bottle coal or weak caking coal can not be separately as the coal of using of coking, and have only 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: place coal that destructive distillation can generate tar, coke-oven gas and semicoke under the temperature about 600 ℃.The elementary composition of semicoke mainly is carbon, hydrogen and oxygen, and nitrogen in the raw coal and element sulphur be almost most of consumption in pyrolytic process, and a spot of nitrogen, element sulphur are present in the semicoke with the form of heterogeneous ring compound.The carbon proportion reaches 95% in the semicoke, can be used to produce ferrosilicon and calcium carbide etc.
4. Direct Hydrogenation liquefaction: coal, catalyzer and solvent oil are mixed, under HTHP, make destruction of organic material in the coal, be converted into low molecule liquid state and gaseous product with the hydrogen effect.But DCL/Direct coal liquefaction is technological immature, and investment is quite high, and running cost is also quite big.
At present, be directed to incoherence or weak caking coals such as brown coal, long-flame coal, bottle coal, also lack a kind of comprehensively deep processing method, to utilize dross coal or weak caking coal better.
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 middle low-temperature pyrolysis reaction, generates coal gas, semicoke and coal tar; B1) through transformation absorption the hydrogen in the said coal gas is proposed; B2) said semicoke is sent into gazogene, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in gazogene, and said synthetic gas comprises carbon monoxide and hydrogen; Perhaps said semicoke being sent into circular fluid bed generates electricity; B3) said coal tar is carried out the normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and the tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running at the bottom of the tower; Carbolic oil carries out the carbolic oil extracting and obtains phenols and dephenolize oil; C) with 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: at first, under middle low temperature, dross coal or weak caking coal is carried out middle low-temperature pyrolysis, generates semicoke, coal gas and coal tar; Respectively these three kinds of destructive distillation products are handled then, the first, with semicoke through being gasificated into synthetic gas; Then synthetic gas is carried out the synthetic preparation of fischer-tropsch paraffin class hydro carbons, the second, utilize pressure swing adsorption that the hydrogen in the coal gas is proposed; The 3rd, coal tar is carried out fractionation, fractionation obtains oil at the bottom of carbolic oil, overhead oil and the tower; Carry out extracting again for carbolic oil; Obtain phenols and dephenolize oil, heavy oil at the bottom of the tower and dephenolize oil are carried out delayed coking, obtain coking gas, coking naphtha, coker gas oil, wax tailings and coke; Then, utilize extractive hydrogen that paraffin hydro carbons and coking naphtha, coker gas oil, wax tailings are carried out hydrotreatment; At last, the hydrogenation output that obtains is respectively mixed.In the such scheme, all relate to the hydrogenation process of coal tar, but hydrogenation process is single, concerning the very poor coal tar of quality, can't reaches satisfied effect.
CN93107496.7 provides a kind of method of producing diesel oil by middle coalite tar, and promptly the direct chemical purifying method is handled the diesel oil distillate of coal tar with the method for removal of impurities-refining-washing-breakdown of emulsion-allotment, and refining goes out to reach the diesel oil of request for utilization.CN94112466.5 relates to the method for processing diesel oil with coal tar, and coal tar is main raw material, adds auxiliary material, through mixing stirring, catalyzed oxidation-distillation and synthetic three technological processs, can obtain 0-35# diesel oil.CN88105117 has introduced a kind of prescription and compound method thereof of fuel reagent replacing diesel, and its product only acts as a fuel, and is not suitable for oil motor.These methods all are that coal tar is carried out chemical treatment, poor product quality, and the clean cargo yield is low, does not reach the comprehensive utilization to tar resource.
Hydrogen addition technology is the effective ways that improve the coal tar quality, and in the presence of hydrogenation catalyst, coal tar and hydrogen react, and removes impurity or further conversion in the coal tar.The hydrogen cracking of coal tar is the effective means that is processed as the high quality light ends with coal tar.In general; Hydrocracking technology comprises two sections serial hydrocrackings, one-stage serial hydrocracking and single-stage hydrocracking technology; Two-stage hydrocracking earlier will remove and separate under the unifining condition the deleterious material of hydrocracking catalyst, carry out hydrocracking reaction then; One-stage serial hydrocracking uses the hydrocracking catalyst of anti-ammonia, and first raw material through the hydrofining reaction district, is converted into ammonia with the nitrogen organic in the raw material earlier, and the hydrofining reaction product reacts without separating the direct hydrogen cracking section that gets into; Single-stage hydrocracking uses the hydrocracking catalyst with anti-organic nitrogen compound, and raw material need not unifining and directly carries out hydrogen cracking.
For coal tar raw material; Because contain more nitrogen, sulphur, oxygen impurities in the raw material, these impurity can be converted into ammonia, hydrogen sulfide and water when hydrotreatment, these materials have tangible 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 can't be through the regeneration restorability.Therefore, the hydrogen cracking of coal tar raw material adopts two-stage method more suitable, and first section is the hydrotreatment section, and second section is the hydrogen cracking section, and the reaction product of hydrotreatment section gets into second section hydrogen cracking section after removing impurity.Owing to adopt the two-stage hydrocracking technology; Therefore, how organic cooperation between two sections, just can reach cut down the consumption of energy, prolong catalyzer work-ing life, net effect such as improve the quality of products; Improve the competitive power of production equipment, need be on technology, aspects such as engineering and catalyzer carry out technological innovation.
Contain lighting end (mainly being diesel oil distillate) and last running in the coal tar, for the processing of lighting end, prior art has more suitable processing technology, the 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.Need only in the prior art at present and adopt two-stage hydrocracking to handle last running, or last running is handled in coking.When adopting two-stage hydrocracking to handle last running; Topmost problem is to contain in the last running more materials such as condensed-nuclei aromatics; Particularly be easy to coking on the hydrocracking catalyst surface on the hydrogenation catalyst surface, the work-ing life of catalyzer is shorter, even the method that will the heaviest cut cuts out through methods such as underpressure distillation at present; Still be not enough to guarantee the long-term operation of hydroeracking unit; Because a transformation efficiency of hydroeracking unit is generally about 30%～70%, unconverted last running need constantly circulate in hydroeracking unit, and the constantly accumulation in working cycle of macromole condensed-nuclei aromatics; Cause the obstruction of some cyrogenic equipment on the one hand, have a strong impact on the work-ing life of hydrocracking catalyst on the other hand.
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 normal pressure distillation and/or underpressure distillation; Coal tar lighting end and optional distillate are with after hydrogen mixes; Get into first hydroconversion reaction zone and Hydrobon catalyst contact reacts; Its reaction effluent gets into 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 obtains diesel oil distillate and naphtha fraction after cooling, separation and fractionation.The lighting end that has only utilized coal tar of this method, cut point are 300～380 ℃, and the last running that promptly surpasses diesel oil distillate does not all obtain utilizing, and the utilization ratio of coal tar is low.
CN101629099A discloses a kind of two-stage method coal tar hydro-conversion method.The coal tar hydro carbons partly is converted into the conventional boiling point of institute's hydrocarbon-containifirst in unifining and all is lower than 370 ℃ hydrofining reaction elute and obtains at least one hydrofining diesel oil through separating; At least a portion hydrofining diesel oil partly is converted into the hydro-upgrading reaction effluent and obtains hydro-upgrading diesel oil through separating at hydro-upgrading.The boiling point that this method only is used in coal tar is lower than 370 ℃ cut, and the coal tar utilization ratio is low.
CN102051222A discloses the high nitrogen high aromatic oil of a kind of two-stage method hydrogenating conversion process; One section cold high score oil 1LL wax oil cut content of first raw material hydrocarbon is lower, and it is two section first reaction zone reaction effluent 2R1P that one section cold high score oil 1LL gets into two section first reaction zone 2R1 completion diesel oil hydrogenation modification reaction conversion; When two section first reaction zone 2R1 passed through in one section cold high score gas series connection of at least a portion, formed the full serial flow of high-pressure section; Further; Separate main by treating that the hydrocarbon stream 2FHP that the crackene component is formed gets into the 3rd hydroconversion reaction zone 3R that uses hydrocracking catalyst that 2R1P obtains, the 3rd hydrogenation reaction effluent 3RP mixes with 2R1P or gets into reaction zone 2R1 or get into one stage hydrofining reaction zone 1R.This method also is 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 the coal tar utilization ratio still needs further to improve.
CN102031146A discloses a kind of two-stage method high aromatic oil hydrogenating conversion process; One-stage hydrogenation generates oily heavy cracking stock and reacts with the reduction second pyrolysis through placed in-line two section first reaction zone 2R1 (high boiling fraction hydrocracking reaction district) and two sections Unicracking-JHC reaction zone 2RU (low boiler cut cracking reaction district) at two sections, 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; The one-stage hydrogenation reaction effluent can separate respectively or combined separation with two sections section hydrogenation reaction effluents; Can secondary hydrogenation be generated the heavy cracking stock of oil and introduce 2R1, can the light cracking stock of secondary hydrogenation generation oil be introduced 2RU and realize the circulation cracking.Though heavy cracking stock circulation cracking can improve the output that coal tar is produced light Fuel, the condensed-nuclei aromatics content of coal tar is high, and is particularly heavily higher in the cracking recycle stock, and can constantly accumulate, and causes the 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 first raw material hydrocarbon generates oily last running and reacts to reduce second pyrolysis through placed in-line two section first reaction zone 2R1 (high boiling fraction cracking reaction district) and two section second reaction zone 2RU (diesel modifying reaction zone) at two sections, and one-stage hydrogenation reaction effluent and two sections section hydrogenation reaction effluents carry out combined separation; Can partial hydrogenation be generated oily lighting end 1LBO (diesel oil distillate with or naphtha fraction, be generally the heavy gas oil cut) and introduce diesel modifying reaction zone 2RU; Can be between two sections devices of the independent fractionation of the separating of oil part of hot high score hot high score oil with or one section hot high score oil of device obtain high boiling fraction and get into cracking and hydrogenation cracking reaction district 2R1 circulation cracking, thereby utilize hot high score hydrogenated oil to be accomplished the effect of initial gross separation.This 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
Deficiency to above-mentioned 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, and this technology is through the technique means such as optimum combination of flow process, when improving coal tar production light-weight fuel oil yield; Prolong the work-ing life of catalyzer, improve the running period of 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 middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of said middle low-temperature pyrolysis reaction is 450～700 ℃;
B) described coal tar adopts following method to handle:
(b1) oil gas that obtains of coal tar raw material, delayed coking reaction separates the liquid phase that obtains with part steps (b4) HP separator at least and gets into distillation tower jointly, distills out oil at the bottom of naphtha fraction, carbolic oil cut, wax oil cut and the tower; Naphtha fraction and hydrogen are mixed into petroleum naphtha hydrogenation refining reaction section, hydrogen exist with the unifining condition under contact with Hydrobon catalyst, carry out hydrofining reaction; Dephenolize that the carbolic oil cut obtains after dephenolize oil is mixed into the hydrotreatment conversion zone with the wax oil cut, hydrogen exist with hydroprocessing condition under contact with hydrotreating catalyst, carry out hydrotreatment and react;
(b2) hydrotreatment conversion zone reaction effluent carries out gas-liquid separation, and isolating liquid phase gets into fractionation plant, and fractionation is lighting end and last running;
(b3) last running that obtains of step (b2) at least part get into the hydrocracking reaction section, hydrogen exist with hydrocracking condition under contact with hydrocracking catalyst, carry out hydrocracking reaction;
(b4) hydrocracking reaction section reaction effluent gets into HP separator, is separated into gas phase and liquid phase, and liquid phase at least partly gets into the distillation tower of step (b1);
(b5) the oily delayed coking unit that gets at the bottom of the tower that step (b1) distillation obtains, the distillation tower that the oil gas that delayed coking unit obtains gets into step (b1) distills processing.
In the inventive method, can also comprise the steps:
C1) through pressure swing absorption process the hydrogen in the said coal gas is separated; The hydrogen that obtains can be used for the hydrogenation process of step b).
C2) said semicoke is sent into gazogene, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in gazogene, and said synthetic gas comprises carbon monoxide and hydrogen; Utilize said synthetic gas to carry out F-T synthesis reaction and produce the paraffin class hydro carbons.The coke that delayed coking unit obtains also can get into this gazogene.
In the inventive method step a), dross coal or weak caking coal are one or more in brown coal, long-flame coal and the 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 getting into distillation tower, like dehydration, processing such as solid impurity are taken off in desalination.
In the inventive method step (b1), the final boiling point of the naphtha fraction that distillation tower distills out is 150～190 ℃, is preferably 160～180 ℃; The over point of wax oil cut is generally 270～400 ℃, is preferably 270～350 ℃, and the final boiling point of wax oil cut is generally 480～700 ℃, is preferably 530～650 ℃; The carbolic oil cut is the distillate between naphtha fraction and the wax oil cut.
In the inventive method step (b1), the unifining condition of naphtha fraction is generally: volume space velocity 0.3～3.5h when 180～380 ℃ of temperature of reaction, pressure 3.0～10.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1Preferred hydroprocessing condition is: volume space velocity 0.5～2.0h when 200～360 ℃ 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 ℃ of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1Preferred hydroprocessing condition is: volume space velocity 0.2～0.8h when 200～400 ℃ 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 preferably is lower than hydrotreatment reaction pressure 5～12MPa.The hydrofining reaction section is preferably used hydrogen single pass flow process, and the hydrofining reaction elute is after gas-liquid separation, and liquid phase is a petroleum naphtha behind the hydrogenation, and gas phase is used for the hydrogen make-up of 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 generally are carrier with the aluminum oxide, are active ingredient with among Mo, W, Co and the Ni one or more, and catalyzer carried out routine and vulcanizes before using, make active ingredient be converted into sulphided state.Can contain suitable auxiliary agent in the catalyzer, like among Si, P, F, Ti, Zr, the B etc. one or more.Active component content in oxide weight in the 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 unifining section and hydrotreatment section can use a kind of, also can use two or more.Reaction mass can contact with protective material before unifining or hydrotreatment, and the protective material consumption is generally 10%～100% of Hydrobon catalyst or hydrotreating catalyst volume.Reaction conditions when reaction mass contacts with protective material such as temperature, pressure, hydrogen to oil volume ratio etc. can be basic identical with unifining or hydroprocessing condition; Also can be different, preferable reaction temperature can be lower than 10～100 ℃ of unifining or hydrotreating reactors.Protectant active ingredient (one or more among Mo, W, Co and the 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 a kind of, preferably is provided with 2～5 kinds, and every kind of protectant consumption is at least 15% of a protective material TV consumption.Pore volume by the agent of Flow of Goods and Materials direction protection reduces successively, and active component content increases successively, to improve the integrated protection effect.Protective material can be arranged on separately in the reactor drum, also can all or part ofly be arranged in the same reactor drum with hydrotreating catalyst (or Hydrobon catalyst).Protective material described in the application is carrier with the aluminum oxide, has an amount of active ingredient, has the impurity of taking off such as demetalization impurity function, handles catalyzer with the protection follow-up hydrogenation, and therefore protectant notion has comprised Hydrodemetalation catalyst in the 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 are generally in 170～360 ℃ of scopes, preferably in 200～300 ℃ of scopes.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), the hydrocracking reaction condition is generally: volume space velocity 0.1～1.2h when 350～445 ℃ of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 500:1～5000:1 and liquid
-1The most preferred reaction conditions of hydrogen cracking is following: volume space velocity 0.2～0.8h when 375～425 ℃ 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 conventional hydrocracking catalyst in this area, and hydrocracking catalyst generally comprises cracking component and hydrogenation component, and other components such as aluminum oxide, auxiliary agent.Wherein cracking component is at least a in molecular sieve and the amorphous aluminum silicide; The weight content of cracking component in hydrocracking catalyst is generally 20%～70%; Be preferably 30%～60%; Molecular sieve is generally the Hydrogen Y molecular sieve, modification Hydrogen Y molecular sieve, and the weight content of silicon-dioxide is generally 15%～55% in the amorphous aluminum silicide.Hydrogenation component is one or more among Mo, W, Co and the Ni, is generally 15%～40% in the content of oxide weight in catalyzer, 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 the hydrocracking process, can replenish an amount of sulphur or sulfocompound as required, in reaction process, handle in activity sulphided state preferably to keep hydrotreating catalyst and hydrocracking catalyst.
In the step of the present invention (b3), preferably replenish an amount of NH in the reaction mass off and on
3, replenish NH
3In the process, NH
3Concentration in the reaction system gaseous phase materials is 100～2000 μ g/g, is preferably 300～800 μ g/g and (mends NH
3Method is: replenish liquefied ammonia at reactor inlet; Analytical procedure is: the reactor outlet gaseous phase materials is analyzed).Replenish NH
3Can every running carry out once in preferred 5～30 days on the 1st～100, carried out 1～12 hour at every turn.Can reduce the hydrocracking catalyst carbon deposit like this, increase the service life.Replenish NH
3Process in the preferred hydrogen to oil volume ratio that increases operation, improve 200～1000 in the time of for example can be than normal running.
In the step of the present invention (b4), the isolated liquid phase of HP separator also can partly get into the fractionation plant in (b2).HP separator adopts cold high pressure separator; The service temperature of cold high pressure separator is generally 40～80 ℃, and working pressure identical with the hydrocracking reactor working pressure (ignoring the pressure-losses) adopts cold high pressure separator can significantly reduce number of devices; Simplify flow process, reduce investment.
In the inventive method step (b5), 450 ℃～550 ℃ of delayed coking reaction temperature, reaction pressure 0.1MPa～0.5MPa; 485 ℃～535 ℃ of preferable reaction temperature, preferred reaction pressure 0.15MPa～0.35MPa.Delayed coking reaction product and coking raw material adopt a cover 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 hydrogen cracking section can be provided with the recycle hydrogen system respectively, also can adopt a cover recycle hydrogen system.When adopting a cover recycle hydrogen system, the gas phase after the gas-liquid separation of hydrotreatment section reaction effluent gets into the hydrogen cracking section after removing impurity, and the gas phase after the gas-liquid separation of hydrogen cracking section reaction effluent is circulated to the hydrotreatment section and recycles.
In the inventive method step (b1), the dephenolize of carbolic oil cut all can be adopted this area ordinary method.For example dephenolize is handled and is adopted the soda acid method for extracting, specifically can adopt conventional coal tar carbolic oil refining plant, and the carbolic oil cut gets into extraction tower, in extraction tower, adds alkaline solution, and the phenates that extracting goes out is through steaming stripping oil, sulfuric acid or CO
2Decompose the back and obtain phenol products, extracting obtains dephenolize oil after going out phenol products.
In the inventive method step (c1), transformation absorption recover hydrogen is this area ordinary method, and is for example specific as follows:
Transformation absorption perhaps is called the transformation adsorption separation technology; Be based on the physical adsorption principle for balance of gas on solid adsorbent; With sorbent material under the different pressures condition to mixture in the difference of different components equilibrium adsorption capacity be the basis; Under high pressure adsorb, desorption under low pressure, thus realize the chemical industry cyclical operation process of mixture separation.The typical process of the transformation absorption of coal gas does; Coal gas is raised to the required pressure of absorption through gas compressor with pressure; Make temperature of gas reach the desired temperature of absorption through cooling system again; Heavy hydrocarbon impurity in the coal gas (like tar, benzene and naphthalene etc.) will be adsorbed in the preadsorption system, and the coal gas of rough purification carries out impurity absorption through adsorption system again, and more purified hydrogen comes out from adsorber.
Preferably, in the 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, said coal gas is at high temperature contacted with water.Also contain carbon monoxide in the coal gas; For carbon monoxide; What or other that can look the required hydrogen consumption of hydrogenation in the subsequent technique install required amounts of hydrogen judge its whether adopt in changes technology with its again with water reaction generation hydrogen; The hydrogen that becomes in the carbonic oxide can adopt pressure swing adsorption to propose with the hydrogen that the dry distillation of coal produces, be used for the feed hydrogen of hydrogenation reaction.In to become technology be exactly the technology of carbon monoxide and water reacted hydrogen of making, this is well known to those skilled in the art, and repeats no more here.
Coal gas can suitably purify before carrying out transformation absorption.
In the inventive method step (c2), semicoke is used to produce coal gas and belongs to this area routine techniques, and for example detailed process is following:
At first, in gazogene, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash.Synthetic gas comprises carbon monoxide and hydrogen.Gazogene can be fixed-bed type, thermopnore formula and fluidized bed type, preferably uses the fluidized bed type gazogene.Preferably, the reaction pressure of fluidized bed type gazogene is 0.1MPa～4.5MPa, and temperature of reaction is 650 ℃～1100 ℃, and the gas-solid volume ratio is 3～8; More preferably, the reaction pressure of fluidized bed type gazogene is 0.1MPa～3.5MPa, and temperature of reaction is 700 ℃～1000 ℃, and the gas-solid volume ratio is 4～8.In this step, the volume ratio of oxygen and water vapour is 3～9.
Then, synthetic gas prepares the paraffin class hydro carbons through F-T synthesis reaction.F-T synthesis reaction is a method well known to those skilled in the art.Concrete next under appropriate reaction conditions, the volume ratio of adjustment hydrogen and carbon monoxide, under the high-selectivity catalyst effect, the distribution of adjustment reaction product, its primitive reaction is that carbon monoxide and hydrogen addition generate hydro carbons.The 6th chapter of " 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 attitude bed formula F-T synthesis reaction device; More preferably, the temperature of reaction of F-T synthesis reaction is 120 ℃～450 ℃, and reaction pressure is 0.05MPa～10MPa, and synthetic gas is 100h to the volume space velocity of reactor volume
-1～5000h
-1Most preferably, the temperature of reaction of F-T synthesis reaction is 150 ℃～100 ℃, and reaction pressure is 0.1MPa～10MPa, and synthetic gas volume air speed is 200h
-1～5000h
-1Utilize above-mentioned technology; Not only well solved the liquefaction of semicoke; Cetane value that the more important thing is the oil product of producing after the synthetic paraffin class hydro carbons of producing of fischer-tropsch is through hydrotreatment is generally about 60～70; Can further promote the cetane value that the 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 simultaneously with coal tar, also can adopt independent hydrogenation unit to handle.
Compared with prior art, the present invention has following advantage:
1. the fractionation of coal tar raw material, the fractionation and the living olefiant fractionation of hydrogen cracking of pyrogenic reaction oil gas are become one, simplified flow process, facility investment is low, has made full use of the heat of pyrogenic reaction high-temperature oil gas, effectively reduces energy consumption.Coking naphtha cut and hydrogen cracking naphtha fraction do not get into the hydrotreatment conversion zone of last running; Adopt independent hydrofining reaction section to handle; Help reducing facility investment (unifining section required reaction pressure lower), improved the reaction depth (having improved the hydrogen dividing potential drop of hydrotreatment reaction process) that heavy fractioning hydrogenation is handled.The product of hydrotreatment section carries out fractionation to be handled, and the last running that obtains gets into the hydrogen cracking section.Can avoid lighting end that too much scission reaction takes place like this, the purpose product yield is high, and product yields such as the dry gas of low value are low, improved whole economic efficiency.
2. the liquid phase that generates of the hydrocracking reaction branch distillation tower that is circulated to coal tar raw material and coking oil gas distills processing jointly; This flow process is different from the hydrocracking reaction elute and all gets into hydrotreating reactor, and the liquid phase that also is different from the hydrocracking reaction elute all gets into fractionating system and carries out the fractionation processing.This flow process has following advantage: being easy to the macromole condensed-nuclei aromatics of catalyst active center's coking gets into tower in still-process at the bottom of of can producing in the hydrocracking reaction process is oily; And then adopt coker to handle, avoided the macromole condensed-nuclei aromatics to get into hydrogenation unit accelerator activator carbon deposit.Simultaneously, also avoid the light constituent in the hydrocracking reaction elute to get into hydrotreating reactor, improved the hydrogen dividing potential drop in the hydrotreating reactor greatly (if light constituent gets into hydrotreating reactor; Light constituent can be in gas phase state, reduces the hydrogen concentration in the reaction system, has promptly reduced the hydrogen dividing potential drop); Under the constant condition of stagnation pressure, the hydrogen dividing potential drop improves the hydrogenation saturated reaction that helps the hydrogenation reaction in the hydrotreating reactor, particularly condensed-nuclei aromatics; And the condensed-nuclei aromatics hydrogenation saturated after; In follow-up hydrocracking reactor, be easy to carry out hydrocracking reaction, reduced the coking reaction, prolonged the work-ing life of hydrocracking catalyst.Simultaneously; Hydrogen cracking high pressure hot separator liquid phase gets into hydrotreating reactor, can dilute coal tar raw material, reduces the probability of polymerization cokings such as two rare hydrocarbon wherein; Relax the operational condition of hydrotreating reactor, helped prolonging the work-ing life of hydrotreating catalyst.And isocrackate adopts the operating method of high pressure hot separator, also can effectively avoid the macromole condensed-nuclei aromatics to separate out the problem of occluding device.
3. the oil gas of delayed coking generation is together separating in the distillation tower with isocrackate jointly; The naphtha fraction that obtains comprises coking naphtha and hydrogen cracking petroleum naphtha; Both mixed hydrogenations are refining, avoided problem in the independent coking naphtha unifining process, the problem includes: device short problem running period that easy coking causes.
4. in the hydrocracking reactor operating process, preferably replenish an amount of NH off and on
3This operating method can effectively reduce the hydrocracking catalyst carbon deposit, prolongs the work-ing life of hydrocracking catalyst.Find that after deliberation the carbon deposit major cause of hydrocracking catalyst is that wherein condensed-nuclei aromatics is adsorbed on the acidity of catalyst center, constantly assembles polymerization, under hot conditions, the hydrogenation that is not able to do in time, and the polymerization coking reaction has taken place.In the reaction process, in unconverted round-robin operating method, the macromole condensed-nuclei aromatics in the recycle stock not section accumulation increases (generating under the hot conditions) especially, and therefore along with the carrying out of reaction, hydrocracking catalyst has the trend of inactivation quickening.The present invention is through discovering, in the coal tar hydrogenating reaction process, owing to adopt two sections flow processs, the impurity that gets in the hydrocracking reactor is less, through an amount of NH of regular replenishment
3, NH
3Can on the acid sites of hydrocracking catalyst, form competitive adsorption with the macromole condensed-nuclei aromatics, avoid macromole condensed-nuclei aromatics long-time absorption accumulation and then coking on acid sites.NH
3Introducing formed competitive adsorption; The macromole condensed-nuclei aromatics desorption of receiving in the big acidity of absorption is got in the oil phase of reaction system; And the discharge hydrocracking reactor gets into hydrotreating reactor; Catalyst performance in the hydrotreating reactor and reaction conditions are more suitable for the hydrogenation saturated reaction of macromole condensed-nuclei aromatics, and the macromolecular substance after hydrogenation is saturated is easy to take place hydrocracking reaction, and the coking reaction reduces greatly.Therefore, the inventive method can effectively reduce the coking tendency of hydrocracking catalyst, prolongs catalyzer work-ing life.At additional NH
3Process in, suitably strengthen the desorption that hydrogen-oil ratio can effectively improve the macromole condensed-nuclei aromatics, further improve treatment effect.At additional NH
3Process in, the cracking performance of hydrocracking catalyst has decline slightly, per pass conversion only descends 1～2 percentage point, does not influence normal running basically, and the selectivity of intermediate oil increases, the total economy of body is unaffected, stops to replenish NH
3After, reactivity worth is quick-recovery soon.
5. the deep processing method of dross coal provided by the present invention or weak caking coal compared with prior art, the synthetic gas after the semicoke gasification carries out that fischer-tropsch is synthetic to be used to again produce the paraffin class hydrocarbon, and is used for the final production oil product.In addition, in the transformation absorption to hydrogen be used for hydrogenation reaction, also improved the utilization ratio of coal gas.
Description of drawings
Fig. 1 is a kind of concrete process flow diagram of the present invention.Wherein: 1-coal tar raw material, 2-hydrotreating reactor, 3-hydrotreatment reaction effluent gas-liquid separator, 4-separation column; The 5-hydrocracking reactor, 6-recycle hydrogen de impurity device, 7-hydrotreated naphtha cut, 8-diesel oil distillate; The 9-HP separator, 20-hydrogen make-up, 21-distillation tower, 22-delayed coking unit; The 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-unifining petroleum naphtha, 30-dross coal or weak caking coal; 31-dry distillation of coal device, 32-dry distillation gas transformation fractionation by adsorption hydrogen device, 33-semicoke preparing synthetic gas device, the fischer-tropsch synthesizer of 34-synthetic gas system hydrocarbon.
Embodiment
Further specify method of the present invention and effect through specific embodiment below.As shown in Figure 1, low-temperature pyrolysis in dross coal or the weak caking coal process obtains dry distillation gas, coal tar and semicoke; Dry distillation gas adopts pressure swing absorption process to incite somebody to action Hydrogen Separation wherein, and the hydrogen that obtains is used to add the naphtha fraction hydrofining reactor of hydrogen partial; It is master's synthetic gas that semicoke entering gazogene obtains with carbon monoxide and hydrogen, and synthetic gas can adopt the Fischer-Tropsch synthesizer to obtain synthin.A kind of concrete technical process of coal tar hydrogenating part of the present invention is: coal tar raw material and delayed coking oil gas and hydrogen cracking generate the common distillation tower 21 that gets into of oil; Obtain mixing naphtha fraction 26 through distillation and (comprise coking naphtha cut, hydrogen cracking naphtha fraction; And the naphtha fraction in a spot of coal tar), carbolic oil cut; Oil at the bottom of wax oil cut and the tower, oil gets into delayed coking unit 22 at the bottom of the tower.Mix naphtha fraction 26 and get into petroleum naphtha hydrogenation refining reaction section, unifining petroleum naphtha 29 is reclaimed in the reaction back, is good catalytic reforming raw material; Gas phase is used for the hydrotreatment conversion zone after further increasing.The carbolic oil cut carries out the hydrotreatment reaction with the wax oil cut jointly after the dephenolize of dephenolize device; Carry out reactions such as hydrogenating desulfurization, denitrogenation, deoxidation, saturated, the rare hydrocarbon of aromatic hydrocarbons be saturated; Reaction effluent carries out fractionation, obtains diesel oil distillate 8 behind the hydrogenation, and last running gets into the hydrocracking reaction district.The hydrotreatment reaction effluent is after gas-liquid separation, and gas phase is used for hydrocracking reaction after removing impurity.The hydrocracking reaction elute is separated into liquid and gas in HP separator 9, liquid phase loops back distillation tower 21, recycles after the gas phase treatment.
Embodiment 1
The Nanning brown coal are sent to carry out dry distillation reactor in the fluidized bed dry distillation reactor drum, pressure 0.1MPa, 500 ℃ of service temperatures generate coal gas, coal tar and semicoke.The coal tar oil properties is seen table 1.Get into pressure-swing absorption apparatus after the gas purification; Through the adsorption bed of forming by zeolite molecular sieve etc.; Working pressure is 2MPa, with hydrogen proposition wherein, and carbon monoxide component wherein; Become technology in also adopting it has been generated hydrogen with the water reaction again, the hydrogen that produces with the dry distillation of coal adopts pressure swing adsorption to propose to be used for the charging of coal tar hydrogenating unit.Semicoke is then sent into fluidized bed coal gas generator and oxygen, water vapour reaction generation synthetic gas and coal ash.During the semicoke gasification, semicoke and oxygen, water vapour (volume ratio of water vapour, oxygen is 5:l) reaction produce synthetic gas (carbon monoxide and hydrogen) and coal ash; Gazogene reaction pressure 0.13MPa, 900 ℃ 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 gets into the F-T synthesis reaction device, reaction pressure 0.6MPa, and 180 ℃ of temperature of reaction, synthetic gas air speed are 4000h
-1, generating the paraffin class hydrocarbon, the paraffin hydro carbons can get into the hydrocracking reaction section (the unmixed processing of present embodiment) in apparatus of the present invention.
Carry out processing treatment by flow process shown in Figure 1 behind coal tar process off line tool impurity and the water.
Coal tar raw material and delayed coking oil gas and hydrogen cracking liquid product get into separation column, fractionate out naphtha fraction (C5～180 ℃), carbolic oil cut (180～290 ℃), wax oil cut (290～550 ℃).Naphtha fraction carries out unifining, and the carbolic oil cut carries out dephenolize to be handled, and dephenolize oil and wax oil cut carry out hydrotreatment, obtains diesel oil distillate and heavy oil fraction (by 325 ℃ of cuttings) after the hydrotreatment, and heavy oil fraction carries out hydrocracked, treated.Oil gets into delayed coking unit at the bottom of the tower.
The service temperature of delayed coking unit is 510 ℃, and pressure is 0.15MPa.Hydrorefined temperature of reaction device temperature in is 280 ℃, and reaction temperature rising is 80 ℃, volume space velocity 1.5h when reaction pressure is 6.0MPa, hydrogen to oil volume ratio 800:1 and liquid
-1Volume space velocity 0.64h when the temperature of reaction of hydrotreatment is 350 ℃, pressure 15.1MPa, hydrogen to oil volume ratio 1000:1 and liquid
-1Volume space velocity 0.3h when 375 ℃ of the temperature of reaction of hydrogen cracking, pressure 15.9MPa, hydrogen to oil volume ratio 1200:1 and liquid
-1Hydrotreating catalyst is identical hydrogenation catalyst with Hydrobon catalyst, and this hydrogenation catalyst is with alumina supporter, and the molybdenum oxide weight content is 15%, and the Tungsten oxide 99.999 weight content is 12%, and the nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume are 0.35ml/g.Hydrocracking catalyst is conventional hydrocracking catalyst, and (silica weight content is 27% to catalyzer with Y zeolite (the silica molecular ratio is 12, and structure cell is often for 0.2426nm) and amorphous aluminum silicide; Infrared acidity is 0.4mmol/g) be the cracking component, the Y zeolite weight content is 15%, the amorphous aluminum silicide weight content is 35%; The Tungsten oxide 99.999 weight content is 28%; The nickel oxide weight content is 8%, and surplus is an aluminum oxide, and specific surface area is 270m
2/ g, pore volume are 0.42ml/g.Hydrotreating catalyst and hydrocracking catalyst carry out conventional prevulcanized before use to be handled.Turn round after 3000 hours, keep identical transformation efficiency (transformation efficiency is 55% control by the hydrocracking reactor outlet less than 325 ℃ of distillate weight yields, down together) and need 8 ℃ of temperature raisings.The main products quality is seen table 3 (the main products quality behind the coal tar hydrogenating does not contain the synthetic paraffinic hydrocarbon of fischer-tropsch).
Table 1 coal tar main character
Embodiment 2
Carry out dry distillation reactor in the fluidized bed dry distillation reactor drum during the Yilan coal sent to, pressure 0.12MPa, 600 ℃ of service temperatures generate coal gas, coal tar and semicoke.The coal tar oil properties is seen table 2.Dry distillation gas purifies the back and gets into pressure-swing absorption apparatus; Through the adsorption bed that constitutes by silica gel etc.; Working pressure is 2.45MPa, with hydrogen proposition wherein, and carbon monoxide component wherein; Become technology in also adopting it has been generated hydrogen with the water reaction again, the hydrogen that produces with the dry distillation of coal adopts pressure swing adsorption to propose to be used for the charging of coal tar hydrogenating unit.Semicoke is then sent into fluidized bed coal gas generator and oxygen, water vapour reaction generation synthetic gas and coal ash.During the semicoke gasification, semicoke and oxygen, water vapour (volume ratio of water vapour, oxygen is 3:l) reaction produce synthetic gas (carbon monoxide and hydrogen) and coal ash; Gazogene reaction pressure 3MPa, 750 ℃ 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 gets into the F-T synthesis reaction device, reaction pressure 7.5MPa, and 300 ℃ of temperature of reaction, synthetic gas air speed are 300h
-1, generate the paraffin class hydrocarbon.
The hydrogenation technique of coal tar is identical with embodiment 1.
Table 2 destructive distillation coal tar main character
With embodiment 2, hydrotreatment section temperature of reaction is 350 ℃, uses the hydrogenation protecting agent to carry out pre-treatment before the hydrotreatment section; The hydrogenation protecting agent is conventional hydrogenation protecting agent, is carrier with the aluminum oxide, contains molybdenum oxide 6%; Powder blue 1%, pore volume are 0.82mL/g, and specific surface area is 128M
2/ g.The treatment condition of hydrogenation protecting agent are temperature of reaction volume space velocity 1.2h when being 310 ℃, pressure 15.1MPa, hydrogen to oil volume ratio 1200:1 and liquid
-1Other is identical with embodiment 2.
Press the method for embodiment 3, scheme one: every running 6 days, hydrocracking reactor replenishes 2 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 300 μ g/g, after 1500 hours, keeps identical transformation efficiency and needs 1 ℃ of temperature raising.Turn round after 3000 hours, keep identical transformation efficiency and need 1 ℃ of temperature raising again.Scheme two: every running 30 days; Hydrocracking reactor replenishes 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, keep identical transformation efficiency and need 2 ℃ of temperature raisings.Turn round after 3000 hours, keep identical transformation efficiency and need 1 ℃ of temperature raising again.
Comparative example 1
Press the method for embodiment 1, the hydrocracking reaction elute does not get into water distilling apparatus, and all gets into hydrotreating reactor.Turn round after 3000 hours, keep identical transformation efficiency and need 25 ℃ of temperature raisings.
Comparative example 2
Press the method for embodiment 4, hydrocracking reactor is not mended the ammonia operation, turns round after 1500 hours, and when keeping identical transformation efficiency, temperature of reaction need promote 5 ℃.Turn round after 3000 hours, keep identical transformation efficiency and need 4 ℃ of temperature raisings once more.
Table 3 the inventive method main products character
| The product main character | Embodiment 1 | Embodiment 2 | |
|
| 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 (10)
1. the deep processing method of dross coal or weak caking coal is characterized in that comprising the steps:
A) dross coal or weak caking coal are carried out middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of said middle low-temperature pyrolysis reaction is 450～700 ℃;
B) described coal tar adopts following method to handle:
(b1) oil gas that obtains of coal tar raw material, delayed coking reaction separates the liquid phase that obtains with part steps (b4) HP separator at least and gets into distillation tower jointly, distills out oil at the bottom of naphtha fraction, carbolic oil cut, wax oil cut and the tower; Naphtha fraction and hydrogen are mixed into petroleum naphtha hydrogenation refining reaction section, hydrogen exist with the unifining condition under contact with Hydrobon catalyst, carry out hydrofining reaction; Dephenolize that the carbolic oil cut obtains after dephenolize oil is mixed into the hydrotreatment conversion zone with the wax oil cut, hydrogen exist with hydroprocessing condition under contact with hydrotreating catalyst, carry out hydrotreatment and react;
(b2) hydrotreatment conversion zone reaction effluent carries out gas-liquid separation, and isolating liquid phase gets into fractionation plant, and fractionation is lighting end and last running;
(b3) last running that obtains of step (b2) at least part get into the hydrocracking reaction section, hydrogen exist with hydrocracking condition under contact with hydrocracking catalyst, carry out hydrocracking reaction;
(b4) hydrocracking reaction section reaction effluent gets into HP separator, is separated into gas phase and liquid phase, and liquid phase at least partly gets into the distillation tower of step (b1);
(b5) the oily delayed coking unit that gets at the bottom of the tower that step (b1) distillation obtains, the distillation tower that the oil gas that delayed coking unit obtains gets into step (b1) distills processing.
2. method according to claim 1 is characterized in that also comprising the steps:
C1) through pressure swing absorption process the hydrogen in the said coal gas is separated; The hydrogen that obtains is used for the hydrogenation process of step b).
3. method according to claim 1 and 2 is characterized in that also comprising the steps:
C2) said semicoke is sent into gazogene, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in gazogene, and said synthetic gas comprises carbon monoxide and hydrogen; Utilize said synthetic gas to carry out F-T synthesis reaction and produce the paraffin class hydro carbons.
4. method according to claim 1 is characterized in that: the final boiling point of the naphtha fraction that distillation tower distills out in the step (b1) is 150～190 ℃, is preferably 160～180 ℃; The over point of wax oil cut is 270～400 ℃, is preferably 270～350 ℃, and the final boiling point of wax oil cut is 480～700 ℃, is preferably 530～650 ℃; The carbolic oil cut is the distillate between naphtha fraction and the wax oil cut.
5. method according to claim 1; It is characterized in that: in the step (b1), the unifining condition of naphtha fraction is: volume space velocity 0.3～3.5h when 180～380 ℃ of temperature of reaction, pressure 3.0～10.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1Preferred hydroprocessing condition is: volume space velocity 0.5～2.0h when 200～360 ℃ of temperature of reaction, pressure 4.0～8.0MPa, hydrogen to oil volume ratio 1000:1～2000:1 and liquid
-1
Hydroprocessing condition is in the step (b1): volume space velocity 0.1～1.5h when 180～435 ℃ of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300:1～5000:1 and liquid
-1Preferred hydroprocessing condition is: volume space velocity 0.2～0.8h when 200～400 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～3000:1 and liquid
-1
The hydrocracking reaction condition is in the step (b3): volume space velocity 0.1～1.2h when 350～445 ℃ of temperature of reaction, pressure 8.0～20.0MPa, hydrogen to oil volume ratio 500:1～5000:1 and liquid
-1The most preferred reaction conditions of hydrogen cracking is: volume space velocity 0.2～0.8h when 375～425 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 1000:1～2000:1 and liquid
-1
The delayed coking reaction temperature is 450 ℃～550 ℃ in the step (b5), and reaction pressure is 0.1MPa～0.5MPa; Preferable reaction temperature is 485 ℃～535 ℃, and preferred reaction pressure is 0.15MPa～0.35MPa.
6. method according to claim 1 is characterized in that: in the step (b1), hydrofining reaction pressure is lower than hydrotreatment reaction pressure 5～12MPa; The hydrofining reaction section adopts hydrogen single pass flow process, and the hydrofining reaction elute is after gas-liquid separation, and liquid phase is a petroleum naphtha behind the hydrogenation, and gas phase is used for the hydrogen make-up of hydrotreatment conversion zone through supercharging.
7. method according to claim 1 is characterized in that: in the step (b1), Hydrobon catalyst and hydrotreating catalyst are conventional Hydrobon catalyst and hydrotreating catalyst; Hydrobon catalyst and hydrotreating catalyst are carrier with the aluminum oxide, are active ingredient with among Mo, W, Co and the Ni one or more, and catalyzer carried out routine and vulcanizes before using, make active ingredient be converted into sulphided state; Active component content in oxide weight in the catalyzer is 5%～55%, is preferably 15%～35%;
Hydrocracking catalyst adopts the conventional hydrocracking catalyst in this area in the step (b3); Hydrocracking catalyst comprises cracking component and hydrogenation component; Wherein cracking component is at least a in molecular sieve and the amorphous aluminum silicide; The weight content of cracking component in hydrocracking catalyst is 20%～70%, is preferably 30%～60%; Hydrogenation component is one or more among Mo, W, Co and the Ni, is 15%～40% in the content of oxide weight in catalyzer, is preferably 25%～35%; Hydrocracking catalyst carries out conventional sulfidizing before use, makes active ingredient be converted into sulphided state.
8. according to claim 1 or 7 described methods, it is characterized in that: in the step (b1), reaction mass contacted with protective material before unifining or hydrotreatment, and the protective material consumption is 10%～100% of Hydrobon catalyst or a hydrotreating catalyst volume.
9. method according to claim 1 is characterized in that: in the step (b2), the conventional separation column that fractionation plant comprises, the cut-point of lighting end and last running are in 170～360 ℃ of scopes, preferably in 200～300 ℃ of scopes.
10. method according to claim 1 is characterized in that: in the step (b3), replenish to the reaction mass discontinuous an amount of NH
3, replenish NH
3In the process, NH
3Concentration in the reaction system gaseous phase materials is 100～2000 μ g/g, is preferably 300～800 μ g/g; Replenish NH
3Adopt every running to carry out once in preferred 5～30 days on the 1st～100, carried out 1～12 hour at every turn; Preferably, replenish NH
3Process in hydrogen to oil volume ratio improve 200～1000 during than normal running.
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| CN114763497A (en) * | 2021-01-11 | 2022-07-19 | 中国石油化工股份有限公司 | Biomass hydropyrolysis-gasification co-production process and system |
| CN114763497B (en) * | 2021-01-11 | 2023-01-10 | 中国石油化工股份有限公司 | Biomass hydropyrolysis-gasification co-production process and system |
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