CN102851074A - Combination processing method of coal tar - Google Patents
Combination processing method of coal tar Download PDFInfo
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- CN102851074A CN102851074A CN2012103081444A CN201210308144A CN102851074A CN 102851074 A CN102851074 A CN 102851074A CN 2012103081444 A CN2012103081444 A CN 2012103081444A CN 201210308144 A CN201210308144 A CN 201210308144A CN 102851074 A CN102851074 A CN 102851074A
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- coal tar
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- 238000000034 method Methods 0.000 claims abstract description 82
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Abstract
The invention comprises a combination processing method of coal tar. The method comprises the steps of: the coal tar raw material: (a) introducing a coal tar raw material, delayed coking gas oil and at least part of a liquid phase from a step (d) into a distillation tower, so as to distillate out a light distillate, wax oil and bottom oil; and subjecting the light distillate and the wax oil to a hydrotreating reaction; (b) carrying out gas-liquid separation on an effluent from the hydrotreating reaction, and sending a liquid phase into a fractionation device, so as to distillate out a light fraction and a heavy fraction; (c) carrying out a hydrocracking reaction on at least part of the heavy fraction obtained in the step (b); (d) sending an effluent from the hydrocracking reaction into a hot high pressure separator, so as to separate out a gas phase and a liquid phase; and sending at least part of the liquid phase to the distillation tower in the step (a); and (e) subjecting the bottom oil obtained from distillation in the step (a) to delayed coking, and sending the delayed coking oil gas to the distillation tower in the step (a). Compared with the prior art, the invention method improves the yield of light fuel production from coal tar, prolongs the service life of a catalyst, and increases operation cycle of the device.
Description
Technical field
The present invention relates to a kind of combinational processing method of coal tar, belong to technical field of coal chemical industry.
Background technology
World's crude resources short extremely urgent, and distributed pole is unbalanced, and the storage capacity of coal is very abundant, therefore produces the approach that the vehicle fuel oil product are a kind of necessity with coal.Major technique by the coal liquefaction comprises indirect liquefaction of coal direct liquefaction and coal etc., but these technical costss are high, technical sophistication.Another produces the technology of coke, can be when producing coke, and by-product coal tar, this is the method that extensively adopts at present.But the further processing of coal tar is difficulty relatively, utilize means more single, and price comparison is low, and product outlet also has some setbacks very much, is the waste to existing resource, especially in use environment is had very large impact.
CN93107496.7 provides a kind of method of being produced diesel oil by middle coalite tar, and namely direct chemical refining method is processed 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 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 prescription and compound method thereof of fuel reagent replacing diesel, and its product only acts as a fuel, and is not suitable for diesel engine.These methods all are that coal tar is carried out 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 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 hydrocracking of coal tar is take the effective means of coal tar processing as the high quality light ends.In general, hydrocracking technology comprises two sections 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 the hydrofining condition, then carry out hydrocracking reaction; One-stage serial hydrocracking uses the hydrocracking catalyst of anti-ammonia, and first raw material passes through first the hydrofining reaction district, and the nitrogen organic in the raw material is converted into ammonia, and the hydrofining reaction product directly enters the hydrocracking section without separation and reacts; Single-stage hydrocracking uses the hydrocracking catalyst with anti-organic nitrogen compound, and raw material need not hydrofining and directly carries out hydrocracking.
For coal tar raw material, owing to containing 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 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 can't be by the regeneration restorability.Therefore, the hydrocracking of coal tar raw material adopts two-stage method more suitable, and first paragraph is the hydrotreatment section, and second segment is the hydrocracking section, and the reaction product of hydrotreatment section enters second segment hydrocracking section through behind the imurity-removal.Owing to adopting the 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 on technique, the 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 process last running, or last running is processed in coking.When adopting two-stage hydrocracking to process last running, topmost problem is to contain in the last running the 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 by 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 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 normal pressure distillation and/or underpressure distillation, coal tar lighting end and optional distillate are with after hydrogen mixes, 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, obtain diesel oil distillate and naphtha fraction after separation and the fractionation.The lighting end that has only utilized coal tar of the method, cut point are 300～380 ℃, and the last running that namely surpasses 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.The coal tar hydro carbons is that the conventional boiling point of institute's hydrocarbon-containifirst all is lower than 370 ℃ hydrofining reaction effluent and is isolated at least one hydrofining diesel oil at the hydrofining Partial Conversion; At least a portion hydrofining diesel oil is the hydro-upgrading reaction effluent and is isolated to hydro-upgrading diesel oil at the hydro-upgrading Partial Conversion.The boiling point that the 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, the cold high score oil of a section of the first raw material hydrocarbon 1LL wax oil cut content is lower, and one section cold high score oil 1LL enters two section first reaction zone 2R1 and finishes the diesel oil hydrogenation modification reaction and be converted into two section first reaction zone reaction effluent 2R1P; 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 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 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 to reduce second pyrolysis at two sections 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) by series connection, 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; Secondary hydrogenation can be generated the heavy cracking stock of oil and introduce 2R1, the light cracking stock of secondary hydrogenation generation oil can be introduced 2RU and realize the circulation cracking.Although 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 the first raw material hydrocarbon generates oily last running and reacts to reduce second pyrolysis at two sections two section first reaction zone 2R1 (high boiling fraction cracking reaction district) and two sections second reaction zone 2RU (diesel modifying reaction zone) by series connection, and one-stage hydrogenation reaction effluent and two sections section hydrogenation reaction effluents carry out combined separation; Partial hydrogenation can be generated oily lighting end 1LBO (diesel oil distillate and 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 and or one section 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 finished 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
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: a kind of combinational processing method of coal tar is provided, and when improving coal tar production light-weight fuel oil yield, the work-ing life of extending catalyst, the running period of improving device.
The technical solution adopted for the present invention to solve the technical problems is: a kind of combinational processing method of coal tar is provided, it is characterized in that following steps:
(a) oil gas that obtains of coal tar raw material and delayed coking reaction enters distillation tower jointly, distill out oil at the bottom of benzoline, wax oil and the tower, benzoline and wax oil enter the hydrotreatment conversion zone, hydrogen exist and hydroprocessing condition under contact with hydrotreating catalyst, carry out hydrotreatment and react;
(b) 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;
(c) last running that obtains of step (b) enters the hydrocracking reaction section, hydrogen exist with hydrocracking condition under contact with hydrocracking catalyst, carry out hydrocracking reaction;
(d) hydrocracking reaction section reaction effluent enters high pressure hot separator, is separated into gas phase and liquid phase, and liquid phase enters the distillation tower of step (a);
(e) oil entered delayed coking unit at the bottom of step (a) was distilled the tower that obtains, and the distillation tower that the oil gas that delayed coking unit obtains enters step (a) distills processing;
In the step (a), coal tar raw material is coal-tar heavy oil, middle coalite tar or mixes the raw material in other source; Coal tar raw material is carried out pre-treatment before entering hydrogenation unit, pretreatment process comprises dehydration, desalination and takes off in the solid impurity one or more.
The benzoline that distillation tower described in the step (a) distills out comprises petroleum naphtha and diesel oil, and the final boiling point of wax oil is 450～700 ℃, is preferably 550～650 ℃; In the step (a), hydroprocessing condition is: 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
Hydrotreating catalyst described in the step (a) is conventional hydrotreating catalyst, take aluminum oxide as carrier, in Mo, W, Co and the Ni one or more are as active ingredient, and hydrotreating catalyst vulcanized before using, and made active ingredient be converted into sulphided state; Take the active component content of oxide weight as 5%～55%, be preferably 15%～35% in the hydrotreating catalyst; Reaction mass contacted with protective material before hydrotreatment, and the protective material consumption is 10%～100% of hydrotreating catalyst volume; Protectant active ingredient is one or more among Mo, W, Co and the Ni, and active ingredient is preferably 1%～15% take the content of oxide weight as 0～20%, and the protective material pore volume is 0.4～1.5mL/g, and specific surface area is 20～200m
2/ g.
Hydrotreating catalyst carried out the routine sulfuration before using, make active ingredient be converted into sulphided state.Can contain suitable auxiliary agent in the catalyzer, such as among Si, P, F, Ti, Zr, the B etc. one or more.
Hydrotreating catalyst can use a kind of, also can use two or more.Reaction conditions when reaction mass contacts with protective material such as temperature, pressure, hydrogen to oil volume ratio etc. can be basic identical with hydroprocessing condition, also can be different, can be lower than 10～100 ℃ of hydrotreating reactors such as temperature of reaction.Protective material can use a kind of, preferably arranges 2～5 kinds, and every kind of protectant consumption is at least 15% of protective material cumulative volume 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, also can all or part ofly be arranged in the same reactor with hydrotreating catalyst.Protective material described in the application has an amount of active ingredient take aluminum oxide as carrier, has removing impurities matter such as demetalization impurity function, processes catalyzer with the protection follow-up hydrogenation, and therefore protectant concept has comprised Hydrodemetalation catalyst in the prior art.
The conventional separation column that fractionation plant described in the step (b) comprises, the cut-point of lighting end and last running are in 170～360 ℃ of scopes, preferably in 200～300 ℃ of scopes.
Hydrocracking reaction condition described in the step (c) is: 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 preferred reaction conditions of hydrocracking is as follows: 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
-1In the step (c), 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%, be preferably 30%～60%, hydrogenation component is one or more among Mo, W, Co and the Ni, take the content of oxide weight in catalyzer as 15%～40%, is preferably 25%～35%.
In the inventive method, in hydrotreatment and the hydrocracking process, can replenish as required an amount of sulphur or sulfocompound, in reaction process, process in activity sulphided state preferably to keep hydrotreating catalyst and hydrocracking catalyst.
Replenish to hydrocracking reaction section reaction mass discontinuous described in the step (c) NH
3, replenish NH
3In the process, NH
3Concentration in gaseous phase materials is 100～2000 μ g/g, is preferably 300～800 μ g/g; 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; Wherein replenish NH
3The Hydrogen oil volume improve 200～1000 when comparing normal running.
Enter cold high pressure separator after the isolated gas phase cooling of high pressure hot separator described in the step (d) and separate, the isolated gas phase of cold high pressure separator recycles, and the isolated oil phase of cold high pressure separator enters the fractionation plant of step (b).
The service temperature of the high pressure hot separator described in the step (d) is equal to or less than hydrocracking reaction outlet material temperature, but more than 200 ℃, be preferably 260 ℃ to hydrocracking reaction outlet material temperature, most preferably be hydrocracking reaction outlet material temperature.The service temperature of cold high pressure separator is generally 40～80 ℃.The working pressure of high pressure hot separator and cold high pressure separator identical with the hydrocracking reactor working pressure (ignoring the pressure-losses).
450 ℃～550 ℃ of delayed coking reaction temperature described in the step (e), 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 hydrocracking section can arrange respectively the recycle hydrogen system, 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 enters the hydrocracking section behind imurity-removal, and the gas phase after the gas-liquid separation of hydrocracking section reaction effluent is circulated to the hydrotreatment section and recycles.New hydrogen can add to the hydrotreatment section, also can add to the hydrocracking section.
Described hydrotreating catalyst adopts following method preparation:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that obtains of step (1) mixes with the solution that contains the hydrogenation activity component composition, and then making beating filters, and drying is pulverized;
(3) material that obtains of step (2), moulding, then dry, roasting obtains final Hydrobon catalyst;
Wherein step (1) carborization prepares siliceous aluminium hydroxide and comprises the steps:
A, with sodium aluminate solution in plastic cans, pass into simultaneously and contain CO
2Gas, control pH value to 11.0～13.0, the neutralization reaction time is 1～2 hour;
B, add alkalescence in the material of step a gained and contain silicon materials, add simultaneously 2% ~ 4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained, pass into continuously and contain CO
2Gas, control pH value is 8.0～11.0, the reaction times is 0.5～1.0 hour; It is as follows that alkalescence contains the silicon materials preparation method: with water glass, sodium aluminate, sodium hydroxide and water according to (15～18) Na
2O:Al
2O
3: (15～17) SiO
2: (280～380) H
2The mixed in molar ratio of O is even, makes in 0.5～48 hour in room temperature to 70 a ℃ lower reaction, and alkalescence contains the silicon materials add-on by SiO in the final siliceous aluminium hydroxide
2Weight content is 1%～10%;
C, under the control temperature and pH value of step b, the said mixture blowing air was stablized 1～3 hour;
D, the solidliquid mixture of step c gained is filtered and washing;
The solids drying of e, steps d gained obtains siliceous aluminium hydroxide.
The invention has the beneficial effects as follows:
1. in two-stage hydrogenation technique, the product of hydrotreatment section carries out fractionation to be processed, and the last running that obtains enters the hydrocracking section.Can avoid like this lighting end that too much scission reaction occurs, the purpose product yield is high, and the product yields such as the dry gas of low value are low, improved whole economic efficiency.
2. the hydrocracking reaction effluent carries out gas-liquid separation in high pressure hot separator, liquid phase part wherein or a minute distillation tower that all is circulated to coal tar raw material and coking oil gas distill processing jointly, this flow process is different from the hydrocracking reaction effluent and all enters hydrotreating reactor, and the liquid phase that also is different from the hydrocracking reaction effluent all enters fractionating system and carries out the fractionation processing.This flow process has following advantage: the hot high score liquid phase of (1) hydrocracking reaction effluent directly enters the separation column of coal tar raw material and coking oil gas, because the heat that hot high score liquid phase and coking oil gas bring, make distillation tower substantially need not add heat, namely can realize fractionation process, reduce energy consumption.(2) being easy to the macromole condensed-nuclei aromatics of catalyst active center's coking enters tower in still-process at the bottom of of can producing in the hydrocracking reaction process is oily, and then adopt coker to process, avoided the macromole condensed-nuclei aromatics to enter hydrogenation unit accelerator activator carbon deposit.Simultaneously, also avoid the light constituent in the hydrocracking reaction effluent to enter hydrotreating reactor, greatly improved the hydrogen dividing potential drop in the hydrotreating reactor (if light constituent enters hydrotreating reactor, light constituent can be in gas phase state, reduce the hydrogen concentration in the reaction system, namely reduced the hydrogen dividing potential drop), under the constant condition of stagnation pressure, the hydrogen dividing potential drop improves the hydrogenation reaction that is conducive in the hydrotreating reactor, the hydrogenation saturated reaction of condensed-nuclei aromatics particularly, and the condensed-nuclei aromatics hydrogenation saturated after, in follow-up hydrocracking reactor, be easy to carry out hydrocracking reaction, reduce the coking reaction, prolonged 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 probability of the polymerization cokings such as two rare hydrocarbon wherein, relax the operational condition of hydrotreating reactor, be conducive to prolong 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. in the hydrotreatment conversion zone of the present invention, the preferred optimized hydrotreating catalyst (referring to the application's embodiment part) that uses, this catalyzer has suitable acidity, higher hydrogenation activity, can be saturated to the effective hydrogenation of condensed-nuclei aromatics, the work-ing life that is conducive to improve the follow-up hydrogenation cracking catalyst.
4. the oil gas of delayed coking generation is together separating in the distillation tower jointly with coal tar raw material, can take full advantage of the heat of delayed coking oil gas, reduce energy consumption, greatly reduce facility investment and process cost when respectively fractionation apparatus being set than coal tar raw material and coking oil gas.
5. in the hydrocracking reactor operating process, preferably replenish off and on an amount of NH
3This operating method can effectively reduce the hydrocracking catalyst carbon deposit, prolongs the work-ing life of hydrocracking catalyst.Find 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, and the hydrogenation that is not able to do in time, and the polymerization coking reaction has occured.In the reaction process, special in the operating method of unconverted circulation, the macromole condensed-nuclei aromatics in the recycle stock not section accumulation increases (generating under the hot conditions), therefore along with the carrying out that reacts, and the trend that hydrocracking catalyst has inactivation to accelerate.The present invention is by the research discovery, and in the coal tar hydrogenating reaction process, owing to adopting two sections flow processs, the impurity that enters in the hydrocracking reactor is less, by an amount of NH of regular replenishment
3, NH
3Can form competitive adsorption at the acid sites of hydrocracking catalyst 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 large acidity of absorption is entered in the oil phase of reaction system, and the discharge hydrocracking reactor enters hydrotreating reactor, catalyst performance in the 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 the coking reaction reduces greatly.Therefore, the inventive method can effectively reduce the coking tendency of hydrocracking catalyst, extending catalyst work-ing life.At additional NH
3Process in, suitably strengthen the desorption that hydrogen-oil ratio can Effective Raise macromole condensed-nuclei aromatics, further improve treatment effect.At additional NH
3Process in, the cracking performance of hydrocracking catalyst slightly has decline, per pass conversion only descends 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 to replenish NH
3After, reactivity worth is quick-recovery soon.
Description of drawings
Fig. 1 is process flow sheet of the present invention;
1 is coal tar raw material among the figure; 2 is hydrotreating reactor; 3 are hydrotreatment reaction effluent gas-liquid separator; 4 is separation column; 5 is hydrocracking reactor; 6 is recycle hydrogen de impurity device; 7 is naphtha fraction; 8 is diesel oil distillate; 9 is high pressure hot separator; 10 is cold high pressure separator; 11 is hydrogen make-up; 12 is externally discharged waste water; 13 is distillation tower; 14 is delayed coking unit; 15 are benzoline; 16 is wax oil; 17 is coking oil gas.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described further:
Hydrotreating catalyst most preferably adopts following method preparation in the inventive method:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that obtains of step (1) mixes with the solution that contains the hydrogenation activity component composition, and then making beating filters, and drying is pulverized;
(3) material that obtains of step (2), moulding, then dry, roasting obtains final Hydrobon catalyst.
Wherein step (1) carborization prepares siliceous aluminium hydroxide and comprises the steps:
A, with sodium aluminate solution in plastic cans, pass into simultaneously and contain CO
2Gas, control pH value to 11.0～13.0, the neutralization reaction time is 1～2 hour;
B, add alkalescence in the material of step a gained and contain silicon materials, add simultaneously 2% ~ 4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained, pass into continuously and contain CO
2Gas, control pH value is 8.0～11.0, the reaction times is 0.5～1.0 hour; It is as follows that alkalescence contains the silicon materials preparation method: with water glass, sodium aluminate, sodium hydroxide and water according to (15～18) Na
2O:Al
2O
3: (15～17) SiO
2: (280～380) H
2The mixed in molar ratio of O is even, makes in 0.5～48 hour in room temperature to 70 a ℃ lower reaction, and alkalescence contains the silicon materials add-on by SiO in the final siliceous aluminium hydroxide
2Weight content is 1%～10%;
C, under the control temperature and pH value of step b, the said mixture blowing air was stablized 1～3 hour;
D, the solidliquid mixture of step c gained is filtered and washing;
The solids drying of e, steps d gained obtains siliceous aluminium hydroxide.
The above-mentioned carborization of the present invention prepares in the siliceous aluminium hydroxide process, and step a and step b control temperature of reaction are 20 ~ 40 ℃; The concentration of used sodium aluminate solution is 15 ~ 60gAl among the step a
2O
3/ L is preferably 20 ~ 40gAl
2O
3/ L; Contain CO
2The volumetric concentration of gas is 10v% ~ 50v%; The described polymeric surface active agent of step b is one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether, fatty alkanol amide and the polyacrylamide, and the molecular weight of above-mentioned polymeric surface active agent is 1.8～2.3 ten thousand; The described washing of step c is to be washed till neutrality with 40 ~ 90 ℃ deionized water; The described drying conditions of step e is 110 ~ 130 ℃ of dryings 4 ~ 10 hours; The pH value of step a control reaction end is 11.5～12.0, and step b control pH value is constant to be 10.0～11.0; The constant pH value of step b control hangs down 0.3 ~ 4.0 than the pH value of step a control reaction end, is preferably low 1.0 ~ 2.0.
Coal tar hydrogenating of the present invention is processed in the method for preparing catalyst step (2), the solution that contains the hydrogenation activity component composition is the solution that contains W, Mo, Ni and at least a compound of Co, such as ammonium metawolframate, ammonium molybdate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES etc., drying wherein is lower dry 1 ~ 8 hour at 60 ~ 200 ℃.
In the hydrotreating catalyst preparation method step of the present invention (3), moulding process can add suitable auxiliary agent on demand, such as peptizing agent, extrusion aid, expanding agents etc., peptizing agent, expanding agent, extrusion aid etc. can be materials commonly used in this area, are nitric acid or acetic acid such as peptizing agent, expanding agent is carbon black, tensio-active agent, starch etc., the blue or green powder in extrusion aid such as field etc.Drying process wherein is generally 80 ~ 200 ℃ of dryings 1 ~ 10 hour, and roasting is 350 ~ 500 ℃ of lower roastings 1 ~ 5 hour.
Among the hydrotreating catalyst preparation method of the present invention, can add required suitable auxiliary agent at the arbitrary steps of step (1), (2) to (3).
Coal tar hydrogenating of the present invention is processed in the method for preparing catalyst, and other technology contents is well known to those skilled in the art, such as the preparation of solution, and dry method, the equipment of roasting etc.
Coal tar hydrogenating of the present invention is processed catalyzer take silicon-containing alumina as carrier, and take VIB and VIII metallic element as active ingredient, active ingredient is take the weight content of oxide compound in catalyzer as 25% ~ 60%, the pore volume 0.35cm of catalyzer
3/ g ~ 0.65cm
3/ g, specific surface area is 200m
2/ g ~ 350m
2/ g.
Coal tar hydrogenating of the present invention is processed in the catalyzer, can contain suitable auxiliary agent, and such as Zr, Ti, P etc., auxiliary agent can add in the solid support material preparation process, also can add in catalyst preparation process, and auxiliary agent content is 1% ~ 15%.Coal tar hydrogenating of the present invention is processed in the catalyzer, and active ingredient is one or more among W, Mo, Ni, the Co, preferred following combination: Mo-Ni, Mo-Co-Ni, W-Mo-Co-Ni.Coal tar hydrogenating of the present invention is processed in the catalyzer, and in oxide compound, the weight ratio of group vib active ingredient and VIII family active ingredient is 3:1～10:1.
Coal tar hydrogenating of the present invention is processed in the catalyzer, adopting siliceous containing aluminium is carrier, adopting the siliceous aluminium hydroxide of suitable carborization preparation is the carrier precursor, and hydrogenation activity that can obvious bright high catalyst is particularly to the saturated performance of hydrogenation of macromole condensed-nuclei aromatics.In this siliceous aluminium hydroxide preparation process, add specific alkalescence and contain silicon materials, can improve the acidity of final catalyzer, so when improving Hydrobon catalyst reconstructed coal tar to the hydrogenation and removing reaction of itrogenous organic substance.It is that high alkalinity, suitable silica alumina ratio material obtain after the reaction through suiting that alkalescence contains silicon materials, and this alkalescence contains silicon materials and combines with the process that carborization prepares silicon-containing alumina, has improved the use properties of final hydrogenation catalyst.
The inventive method adopts the siliceous aluminium hydroxide direct impregnation active component solution of not roasting, can greatly improve the content of reactive metal, do not affect the formation of pore volume and specific surface during simultaneously owing to the siliceous aluminium hydroxide shaping and roasting after the dipping active ingredient, therefore, in the hydrotreating catalyst of the inventive method preparation, under the higher prerequisite of active component content, still have larger pore volume and specific surface area.
Further specify method of the present invention and effect below by specific embodiment.As shown in Figure 1, a kind of concrete technology flow process of the present invention is: the liquid phase of coal tar raw material and delayed coking oil gas and hydrocracking high pressure hot separator enters distillation tower 21 jointly, oil at the bottom of distillation obtains lighting end 23, wax oil 24 and tower, oil enters delayed coking unit 22 at the bottom of the tower.Benzoline 23, wax oil 24 and hydrogen enter hydrotreating reactor 2 and carry out the reactions such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation, rare hydrocarbon be saturated.The hydrotreatment reaction effluent is after gas-liquid separation, and gas phase is used for hydrocracking reaction behind imurity-removal; Liquid phase enters the separation column fractionation and obtains naphtha fraction 7, diesel oil distillate 8 and heavy oil fraction, and heavy oil fraction enters hydrocracking reactor 5 and carries out hydrocracking reaction.The hydrocracking reaction effluent is separated into liquid and gas in high pressure hot separator 9, liquid phase circulation returns distillation tower 21, enter cold high pressure separator 10 after the gas phase cooling, the isolated gas phase of cold high pressure separator recycles, the isolated oil phase of cold high pressure separator enters separation column 4 and carries out fractionation, and sewage effluxes from the cold high pressure separator bottom.
Embodiment 1
The low-temperature pyrolysis coal tar of Yilan brown coal, character sees Table 1, after sending pretreatment unit to and removing mechanical impurity and water, enter separation column with the liquid phase of delayed coking oil gas and hydrocracking high pressure hot separator, fractionate out oil and wax oil at the bottom of benzoline (overhead oil), the tower, the initial boiling point of wax oil is 320 ℃, and final boiling point is 670 ℃.Oil enters delayed coking unit at the bottom of the tower.Benzoline and wax oil enter hydrotreater and carry out the hydrotreatment reaction, gasoline fraction and diesel oil distillate that the hydrotreatment reaction obtains can go out device, the heavy distillate that hydrotreatment reaction obtains (between heavy distillate and the diesel oil by 325 ℃ of cuttings) enters hydroeracking unit and carries out hydrocracking reaction, the hydrocracking reaction product is separated into gas phase and liquid phase in high pressure hot separator, liquid phase circulation returns distillation tower.Gas phase enters cold high score separates the gas phase that obtains and loops back hydrotreater, and the oil phase of cold high pressure separator enters the separation column of hydrotreatment reaction product.The service temperature of delayed coking unit is 510 ℃, and pressure is 0.15MPa.Volume space velocity 0.64h when the temperature of reaction of hydrotreatment is 322 ℃, pressure 15.1MPa, hydrogen to oil volume ratio 1000:1 and liquid
-1Volume space velocity 0.3h when 372 ℃ of the temperature of reaction of hydrocracking, pressure 15.9MPa, hydrogen to oil volume ratio 1200:1 and liquid
-1Hydrotreating catalyst is conventional hydrotreating catalyst, and with alumina supporter, 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, (the silica/alumina molecular ratio is as 12 take 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 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 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 processed.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, and is lower same) and need 6 ℃ of temperature raisings.
Prepare hydrotreating catalyst (in oxide weight) by following composition: Mo, 30.0%; W, 8.0%; Ni, 2.5%; Co, 2.0%.
The solution that contains active ingredient is the solution that contains ammonium metawolframate, ammonium molybdate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Peptizing agent is that nitric acid, extrusion aid are that the blue or green powder in field, expanding agent are carbon black.
(1) siliceous aluminium hydroxide preparation.It is 200gAl that solid sodium aluminate is mixed with concentration
2O
3It is 25gAl that the dense sodium aluminate solution of/L, redilution become concentration
2O
3/ L sodium aluminate working solution adds first 10L and contains 25gAl in plastic cans
2O
3/ L sodium aluminate working solution, simultaneously blowing air and pass into the CO that concentration is 45v%
2Gas, 25 ℃ of temperature of reaction, the reaction times is 1 hour, the pH value is reacted at 12.0 o'clock, add alkalescence and contain silicon materials by containing silica weight 5% in the final silyl hydride aluminium, adding simultaneously and adding molecular weight by siliceous aluminium hydroxide weight 3% is 20,000 polyoxyethylene glycol, passes into continuously to contain CO
2Gas remains on about 10.5 the pH of system, 25 ℃ of temperature of reaction, and the reaction times is 1 hour, after question response is complete, stops to pass into CO
2, then blowing air was stablized 60 minutes, and dope filtration also is washed till neutrality with 60 ℃ of deionized waters.Then 120 ℃ of dryings 8 hours, get siliceous aluminium hydroxide Y-1.
Siliceous material preparation method is as follows for its neutral and alkali: with water glass, sodium aluminate, sodium hydroxide and water according to 17Na
2O:Al
2O
3: 16SiO
2: 350H
2The mixed in molar ratio of O is even, makes in 12 hours 45 ℃ of lower reactions.
(2) catalyzer preparation.Siliceous hydroxide Y-1 adds the solution impregnation said mixture material that contains the hydrogenation activity component, then lower dry 2 hours at 120 ℃, add an amount of peptizing agent, account for the blue or green powder in field of siliceous aluminium hydroxide weight 2%, kneading becomes plastic, extruded moulding then, and the stripe shape thing was 120 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, obtain hydrotreating catalyst C-1, the pore volume of catalyzer is 0.58ml/g, and specific surface area is 290m
2/ g.
Other is identical with embodiment 1, and the hydrotreatment section uses C-1 to be hydrotreating catalyst.
Embodiment 3
Raw material is certain mixed coal tar, and main character sees Table 2.Hydrotreatment section temperature of reaction is 350 ℃, uses the hydrogenation protecting agent to carry out pre-treatment before the hydrotreatment section, and the hydrogenation protecting agent is conventional hydrogenation protecting agent, take aluminum oxide as carrier, contains molybdenum oxide 6%, and cobalt oxide 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.
Embodiment 4
Press the method for embodiment 3, scheme one: every running 8 days, hydrocracking reactor replenishes 2 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 350 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 again temperature raising.Scheme two: every running 25 days, hydrocracking reactor replenishes 5 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 750 μ g/g, increases the hydrogen to oil volume ratio of hydrocracking reactor when mending ammonia to 1700:1, 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 again temperature raising.
Comparative Examples 1
Press the method for embodiment 1, the hydrocracking reaction effluent all enters hydrotreating reactor.Turn round after 3000 hours, keep identical transformation efficiency and need 25 ℃ of temperature raisings.
Comparative Examples 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 3 ℃.Turn round after 3000 hours, keep identical transformation efficiency and need 4 ℃ of again temperature raisings.
Table 1 destructive distillation coal tar main character
| Raw material | Middle coalite tar |
| Density (20 ℃), g/cm 3 | 0.9812 |
| Boiling range, ℃ | |
| IBP/10% | 60.8/185.8 |
| 30%/50％ | 236.2/279.0 |
| 70％/90％ | 336.0/436.2 |
| 95％/FBP | 481.0/566.6 |
| S，wt％ | 0.28 |
| N，μg·g -1 | 8976 |
Table 2 mixed coal tar stock oil character
| Stock oil | Main character |
| Density/gcm -3 | 1.12 |
| Boiling range/℃ | 150~600 |
| Carbon residue, wt% | 9.80 |
| Mechanical impurity, wt% | 0.22 |
| Sulphur content/, wt% | 0.35 |
| Nitrogen content, wt% | 1.10 |
| Metal content, μ gg -1 | 152 |
| Oxygen level, wt% | 5.30 |
| Aromaticity content, wt% | 82.5 |
Table 3 the inventive method main products character
| The product main character | Embodiment 1 | |
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 |
| 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 | 44.5 | 45.7 | 41.8 | 41.6 |
* result after turning round 3000 hours by scheme two.
Claims (10)
1. the combinational processing method of a coal tar is characterized in that following steps:
(a) oil gas that obtains of coal tar raw material and delayed coking reaction enters distillation tower jointly, distill out oil at the bottom of benzoline, wax oil and the tower, benzoline and wax oil enter the hydrotreatment conversion zone, hydrogen exist and hydroprocessing condition under contact with hydrotreating catalyst, carry out hydrotreatment and react;
(b) 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;
(c) last running that obtains of step (b) enters the hydrocracking reaction section, hydrogen exist with hydrocracking condition under contact with hydrocracking catalyst, carry out hydrocracking reaction;
(d) hydrocracking reaction section reaction effluent enters high pressure hot separator, is separated into gas phase and liquid phase, and liquid phase enters the distillation tower of step (a);
(e) oil entered delayed coking unit at the bottom of step (a) was distilled the tower that obtains, and the distillation tower that the oil gas that delayed coking unit obtains enters step (a) distills processing;
In the step (a), coal tar raw material is coal-tar heavy oil, middle coalite tar or mixes the raw material in other source; Coal tar raw material is carried out pre-treatment before entering hydrogenation unit, pretreatment process comprises dehydration, desalination and takes off in the solid impurity one or more.
2. working method according to claim 1, it is characterized in that: the benzoline that the distillation tower described in the step (a) distills out comprises petroleum naphtha and diesel oil, and the final boiling point of wax oil is 450～700 ℃, is preferably 550～650 ℃; In the step (a), hydroprocessing condition is: 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
3. working method according to claim 1, it is characterized in that: the hydrotreating catalyst described in the step (a) is conventional hydrotreating catalyst, take aluminum oxide as carrier, in Mo, W, Co and the Ni one or more are as active ingredient, hydrotreating catalyst vulcanized before using, and made active ingredient be converted into sulphided state; Take the active component content of oxide weight as 5%～55%, be preferably 15%～35% in the hydrotreating catalyst; Reaction mass contacted with protective material before hydrotreatment, and the protective material consumption is 10%～100% of hydrotreating catalyst volume; Protectant active ingredient is one or more among Mo, W, Co and the Ni, and active ingredient is preferably 1%～15% take the content of oxide weight as 0～20%, and the protective material pore volume is 0.4～1.5mL/g, and specific surface area is 20～200m
2/ g.
4. working method according to claim 1, it is characterized in that: the conventional separation column that the fractionation plant described in the step (b) comprises, the cut-point of lighting end and last running are in 170～360 ℃ of scopes, preferably in 200～300 ℃ of scopes.
5. working method according to claim 1, it is characterized in that: the hydrocracking reaction condition described in the step (c) is: 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 preferred reaction conditions of hydrocracking is as follows: 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
-1In the step (c), 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%, be preferably 30%～60%, hydrogenation component is one or more among Mo, W, Co and the Ni, take the content of oxide weight in catalyzer as 15%～40%, is preferably 25%～35%.
6. working method according to claim 1 is characterized in that: replenish to the hydrocracking reaction section reaction mass discontinuous described in the step (c) NH
3, replenish NH
3In the process, NH
3Concentration in gaseous phase materials is 100～2000 μ g/g, is preferably 300～800 μ g/g; 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; Wherein replenish NH
3The Hydrogen oil volume improve 200～1000 when comparing normal running.
7. working method according to claim 1, it is characterized in that: enter cold high pressure separator after the isolated gas phase cooling of the high pressure hot separator described in the step (d) and separate, the isolated gas phase of cold high pressure separator recycles, and the isolated oil phase of cold high pressure separator enters the fractionation plant of step (b).
8. working method according to claim 1, it is characterized in that: the service temperature of the high pressure hot separator described in the step (d) is equal to or less than hydrocracking reaction outlet material temperature, but more than 200 ℃, be preferably 260 ℃ to hydrocracking reaction outlet material temperature, most preferably be hydrocracking reaction outlet material temperature.
9. working method according to claim 1 is characterized in that: 450 ℃～550 ℃ of the delayed coking reaction temperature described in the step (e), reaction pressure 0.1MPa～0.5MPa; 485 ℃～535 ℃ of preferable reaction temperature, preferred reaction pressure 0.15MPa～0.35MPa.
10. working method according to claim 1 is characterized in that: described hydrotreating catalyst adopts following method preparation:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that obtains of step (1) mixes with the solution that contains the hydrogenation activity component composition, and then making beating filters, and drying is pulverized;
(3) material that obtains of step (2), moulding, then dry, roasting obtains final Hydrobon catalyst;
Wherein step (1) carborization prepares siliceous aluminium hydroxide and comprises the steps:
A, with sodium aluminate solution in plastic cans, pass into simultaneously and contain CO
2Gas, control pH value to 11.0～13.0, the neutralization reaction time is 1～2 hour;
B, add alkalescence in the material of step a gained and contain silicon materials, add simultaneously 2% ~ 4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained, pass into continuously and contain CO
2Gas, control pH value is 8.0～11.0, the reaction times is 0.5～1.0 hour; It is as follows that alkalescence contains the silicon materials preparation method: with water glass, sodium aluminate, sodium hydroxide and water according to (15～18) Na
2O:Al
2O
3: (15～17) SiO
2: (280～380) H
2The mixed in molar ratio of O is even, makes in 0.5～48 hour in room temperature to 70 a ℃ lower reaction, and alkalescence contains the silicon materials add-on by SiO in the final siliceous aluminium hydroxide
2Weight content is 1%～10%;
C, under the control temperature and pH value of step b, the said mixture blowing air was stablized 1～3 hour;
D, the solidliquid mixture of step c gained is filtered and washing;
The solids drying of e, steps d gained obtains siliceous aluminium hydroxide.
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| CN103205275A (en) * | 2013-04-12 | 2013-07-17 | 大连理工大学 | Method for preparing phenol compound and clean fuel oil from coal tar |
| CN103289740A (en) * | 2013-01-23 | 2013-09-11 | 大连理工大学 | Method for preparing clean fuel oil from coal tar |
| CN103881750A (en) * | 2014-03-17 | 2014-06-25 | 北京宝塔三聚能源科技有限公司 | Coal tar hydrogenation process for maximizing utilization of coal tar residues |
| CN104194828A (en) * | 2014-08-06 | 2014-12-10 | 何巨堂 | Inferior hydrocarbon hydrogenation method comprising reaction heat recycling step |
| WO2015076979A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for hydrotreating a coal tar stream |
| CN106635155A (en) * | 2016-11-03 | 2017-05-10 | 兰州兰石集团有限公司 | Efficient-residual-heat-utilization system for light-fraction conversion of coal tar and method |
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| CN103881750B (en) * | 2014-03-17 | 2015-10-28 | 北京宝塔三聚能源科技有限公司 | A kind of coal tar hydrogenation process of maximum using coal tar residue |
| CN104194828A (en) * | 2014-08-06 | 2014-12-10 | 何巨堂 | Inferior hydrocarbon hydrogenation method comprising reaction heat recycling step |
| CN106635155A (en) * | 2016-11-03 | 2017-05-10 | 兰州兰石集团有限公司 | Efficient-residual-heat-utilization system for light-fraction conversion of coal tar and method |
| CN109536205A (en) * | 2019-01-23 | 2019-03-29 | 陕西东鑫垣化工有限责任公司 | A kind of light tar mixes refining wax oil processing unit (plant) and method |
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