CN102851071B - Two-stage hydrogenation process of coal tar - Google Patents

Two-stage hydrogenation process of coal tar Download PDF

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CN102851071B
CN102851071B CN201210308162.2A CN201210308162A CN102851071B CN 102851071 B CN102851071 B CN 102851071B CN 201210308162 A CN201210308162 A CN 201210308162A CN 102851071 B CN102851071 B CN 102851071B
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reaction
hydrocracking
coal tar
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hydrogenation
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CN102851071A (en
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王小英
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SHANGHAI NEW-UNITY ENERGY TECHNOLOGY CO., LTD.
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王小英
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Abstract

The invention discloses a two-stage hydrogenation process of coal tar. The process comprises the steps of: (a) sending a coal tar raw material into a hydrotreating reaction section, and carrying out a hydrotreating reaction on the coal tar by contacting with a hydrotreating catalyst in the presence of hydrogen and under hydrogenation conditions; (b) carrying out gas-liquid separation on an effluent from the hydrogenating reaction section, and sending a separated liquid phase into the a fractionation device, in order to distillate out a light fraction and a heavy fraction; (c) sending at least part of the heavy fraction from the step (b) into a hydrocracking reaction section, and carrying out a hydrocracking reaction on the heavy fraction by contacting with a hydrocracking catalyst in the presence of hydrogen and under hydrogenation cracking conditions; and (d) sending an effluent from the hydrocracking reaction section into a hot high pressure separator, in order to separate out a gas phase and a liquid phase, and sending at least part of the liquid phase to the hydrotreating reaction section in the step (a). Compared with the prior art, the method provided by the invention 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

Coal tar two-stage hydrogenation processing method
Technical field
The present invention relates to a kind of coal tar two-stage hydrogenation processing method, belong to coal chemical technology.
Background technology
The shortage of world's crude resources is extremely urgent, and distributed pole is unbalanced, and the storage capacity of coal is very abundant, therefore produces with coal the approach that vehicle fuel oil product are a kind of necessity.Comprise the direct liquefaction of coal and the indirect liquefaction of coal etc. by the major technique of coal liquefaction, but these technical costss are high, technical sophistication.Another produces the technology of coke, can be in producing coke, and by-product coal tar, this is the method extensively adopting at present.But the further processing of coal tar is more difficult, utilizes means more single, and price comparison is low, and product outlet also has some setbacks very much, be the waste to existing resource, especially in use environment is had to very large impact.
CN93107496.7 provides a kind of method of being produced diesel oil by middle coalite tar, i.e. direct chemical refining method is processed the diesel oil distillate of coal tar by the method for removal of impurities-refining-washing-breakdown of emulsion-allotment, and refining goes out to reach the diesel oil of service requirements.CN94112466.5 relates to the method with prodn. of diesel for coal tar oil, and coal tar is main raw material, adds auxiliary material, through mix and blend, catalyzed oxidation-distillation and synthetic three technological processs, can obtain 0-35# diesel oil.CN88105117 has introduced a kind of formula and compound method thereof of fuel reagent replacing diesel, and its product, only as fuel, is not suitable for diesel engine.These methods are all that coal tar is carried out to chemical treatment, poor product quality, and light oil yield is low, does not reach the comprehensive utilization to tar resource.
Hydrogen addition technology is the effective ways that improve coal tar quality, and under hydrogenation catalyst exists, coal tar reacts with hydrogen, removes the impurity in coal tar or further transforms.The hydrocracking of coal tar is the effective means taking coal tar processing as high quality light ends.In general, hydrocracking technology comprises two sections of serial hydrocrackings, one-stage serial hydrocracking and single-stage hydrocracking technology, two-stage hydrocracking first will remove and separate the poisonous material of hydrocracking catalyst under hydrofining condition, then carries out hydrocracking reaction; One-stage serial hydrocracking uses the hydrocracking catalyst of resistance to ammonia, and first raw material first passes through hydrofining reaction district, and the nitrogen organic in raw material is converted into ammonia, and hydrofining reaction product directly enters hydrocracking section without separation and reacts; Single-stage hydrocracking uses the hydrocracking catalyst with resistance to organic nitrogen compound, and raw material directly carries out hydrocracking without hydrofining.
For coal tar raw material, owing to containing more nitrogen, sulphur, oxygen impurities in raw material, these impurity can be converted into ammonia, hydrogen sulfide and water in the time of hydrotreatment, these materials have obvious negative effect to follow-up hydrocracking catalyst, particularly water can make the surface acidity irreversibility of hydrocracking catalyst weaken, and then reactivity worth decline, the work-ing life of catalyzer is shorter, and cannot be by regeneration restorability.Therefore, the hydrocracking of coal tar raw material adopts two-stage method more suitable, and first paragraph is hydrotreatment section, and second segment is hydrocracking section, and the reaction product of hydrotreatment section enters second segment hydrocracking section after imurity-removal.Owing to adopting two-stage hydrocracking technology, therefore, how organic cooperation between two sections, just can reach the net effect such as reduce energy consumption, extending catalyst work-ing life, improve the quality of products, improve the competitive power of production equipment, need to be technique, the aspect such as engineering and catalyzer carries out technological innovation.
In coal tar, contain lighting end (being mainly diesel oil distillate) and last running, for the processing of lighting end, prior art has more suitable processing technology, one stage hydrofining technology, and two-stage hydrogenation modification technology etc. all can obtain the product of suitable quality.But for the processing and utilization of last running, prior art does not have suitable method.In currently available technology, need only and adopt two-stage hydrocracking to process last running, or last running is processed in coking.The main deficiency that adopts coking to process last running is to produce burnt amount greatly, and coal tar utilization ratio is low.While adopting two-stage hydrocracking to process last running, topmost problem is to contain in last running the materials such as more condensed-nuclei aromatics, particularly be easy to coking on hydrocracking catalyst surface on hydrogenation catalyst surface, the work-ing life of catalyzer is shorter, even the method by methods such as underpressure distillation, the heaviest cut being cut out at present, still be not enough to ensure the long-term operation of hydroeracking unit, and also can cause the reduction of coal tar utilization ratio, and the increase of operation energy consumption (operation energy consumption of underpressure distillation is higher).
CN101307257A discloses a kind of coal tar hydrogenation modification method of two-stage method, coal tar is cut into coal tar lighting end and coal tar heavy fractioning through air distillation and/or underpressure distillation, after coal tar lighting end and optional distillate mix with hydrogen, enter the first hydroconversion reaction zone and Hydrobon catalyst contact reacts, its reaction effluent enters the second hydroconversion reaction zone after intermediate flash tower or high-pressure stripper remove contained gaseous impurities, with catalyst for hydro-upgrading or hydrocracking catalyst contact reacts, the reaction effluent of gained is through cooling, after separation and fractionation, obtain diesel oil distillate and naphtha fraction.The lighting end that has only utilized coal tar of the method, cut point is 300~380 DEG C, and the last running that exceedes diesel oil distillate is all utilized, and the utilization ratio of coal tar is low.
CN101629099A discloses a kind of two-stage method coal tar hydro-conversion method.Coal tar hydro carbons at hydrofining Partial Conversion for the conventional boiling point of institute hydrocarbon-containifirst all lower than the hydrofining reaction effluent of 370 DEG C and be isolated at least one hydrofining diesel oil; At least a portion hydrofining diesel oil is hydro-upgrading reaction effluent and is isolated to hydro-upgrading diesel oil at hydro-upgrading Partial Conversion.The boiling point that the method is only used in coal tar is lower than the cut of 370 DEG C, and coal tar utilization ratio is low.
CN102051222A discloses the high nitrogen high aromatic oil of a kind of two-stage method hydrogenating conversion process, the cold high score oil of a section of the first raw material hydrocarbon 1LL wax oil cut content is lower, and one section of cold high score oil 1LL enters two section of first reaction zone 2R1 and completes diesel oil hydrogenation modification reaction and be converted into two section of first reaction zone reaction effluent 2R1P; When two section of first reaction zone 2R1 passed through in one section of cold high score gas series connection of at least a portion, form the full serial flow of high-pressure section; Further, separate main by treating that the hydrocarbon stream 2FHP that crackene component forms enters the 3rd hydroconversion reaction zone 3R that uses hydrocracking catalyst that 2R1P obtains, the 3rd hydrogenation reaction effluent 3RP mixes with 2R1P or enters reaction zone 2R1 or enter one stage hydrofining reaction zone 1R.The method is also only applicable to carbolineum or coal-tar base intermediate oil two-stage method hydrogenation process, and hydrogenation last running tail oil can only be used for the oil fuel of low value, and coal tar utilization ratio still needs further raising.
CN102031146A discloses a kind of two-stage method high aromatic oil hydrogenating conversion process, one-stage hydrogenation generates oily heavy cracking stock and reacts to reduce second pyrolysis at two sections of two section of first reaction zone 2R1 (high boiling fraction hydrocracking reaction district) by series connection and two sections of Unicracking-JHC reaction zone 2RU (low boiler cut cracking reaction district), and one-stage hydrogenation generates the light cracking stock 1LBO of oil (light wax oil cut and or heavy gas oil cut) introducing reaction zone 2RU; One-stage hydrogenation reaction effluent can separate respectively or combined separation with two sections of section hydrogenation reaction effluents; Secondary hydrogenation can be generated to the heavy cracking stock of oil and introduce 2R1, the light cracking stock of secondary hydrogenation generation oil can be introduced to 2RU and realize circulation cracking.The output that although heavy cracking stock circulation cracking can improve coal tar produces light Fuel, the condensed-nuclei aromatics content of coal tar is high, particularly heavily higher in cracking recycle stock, and can constantly accumulate, and causes catalyst carbon deposit deactivation rate to accelerate.
CN102021028A discloses a kind of two-stage method high aromatic oil hydrogenating conversion process, the one-stage hydrogenation of the first raw material hydrocarbon generates oily last running and reacts to reduce second pyrolysis at two sections of two section of first reaction zone 2R1 (high boiling fraction cracking reaction district) by series connection and two sections of second reaction zone 2RU (diesel modifying reaction zone), and one-stage hydrogenation reaction effluent and two sections of section hydrogenation reaction effluents carry out combined separation; Partial hydrogenation can be generated to oily lighting end 1LBO (diesel oil distillate and or naphtha fraction, be generally heavy gas oil cut) and introduce diesel modifying reaction zone 2RU; Can be between two sections of devices of the independent fractionation of the separating of oil part of hot high score hot high score oil and or one section of hot high score oil of device obtain high boiling fraction and enter cracking and hydrogenation cracking reaction district 2R1 circulation cracking, thereby utilize hot high score hydrogenated oil to be completed to the effect of initial gross separation.The method does not relate to coking heavy distillate utilization ratio yet and improves, and short problem running period that causes because of coking of hydrocracking catalyst.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: a kind of coal tar two-stage hydrogenation processing method 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 coal tar two-stage hydrogenation processing method is provided, it is characterized in that comprising the steps:
(a) coal tar raw material enters hydrotreatment conversion zone, exists and contacts with hydrotreating catalyst under hydroprocessing condition at hydrogen, carries out hydrotreatment reaction;
(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 step (b) obtains enters hydrocracking reaction section, exists and contacts with hydrocracking catalyst under hydrocracking condition at hydrogen, carries 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 hydrotreatment conversion zone of step (a);
Wherein, in 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 entering before hydrogenation unit, and pretreatment process comprises one or more in dehydration, desalination and de-solid impurity.
In the inventive method step (a), coal tar raw material can be the coal tar raw material of originating arbitrarily, and as coal-tar heavy oil, middle coalite tar also can mix the raw material in other source simultaneously.Coal tar raw material can be carried out conventional pre-treatment entering before hydrogenation unit, as dehydration, and desalination, the processing such as de-solid impurity, wherein de-solid impurity can remove solid impurity wherein and asphalt component by vacuum distillation method or solvent deasphalting method.
Hydroprocessing condition described in step (a) is: volume space velocity 0.1~1.5h when 180~435 DEG C of temperature of reaction, pressure 8.0~20.0MPa, hydrogen to oil volume ratio 300:1~5000:1 and liquid -1; Preferred hydroprocessing condition is: volume space velocity 0.2~0.8h when 200~400 DEG C of temperature of reaction, pressure 10.0~16.0MPa, hydrogen to oil volume ratio 1000:1~3000:1 and liquid -1.
Hydrotreating catalyst described in step (a) is taking aluminum oxide as carrier, and taking one or more in Mo, W, Co and Ni as active ingredient, hydrotreating catalyst vulcanized before using, and made active ingredient be converted into sulphided state; In hydrotreating catalyst, taking the active component content of oxide weight as 5%~55%, be preferably 15%~35%.
Described reaction mass contacted with protective material before hydrotreatment; protective material consumption is 10%~100% of hydrotreating catalyst volume; protectant active ingredient is one or more in Mo, W, Co and Ni; active ingredient is taking the content of oxide weight as 0~20%; be preferably 1%~15%; protective material pore volume is 0.4~1.5mL/g, and specific surface area is 20~200m 2/ g.
Protective material can use one, preferably arranges 2~5 kinds, and every kind of protectant consumption is at least 15% of protective material cumulative volume consumption.Reduce successively by the pore volume of Flow of Goods and Materials direction protection agent, active component content increases successively, to improve integrated protection effect.Protective material can be arranged on separately in a reactor, also can all or part ofly be arranged in same reactor with hydrotreating catalyst.Protective material described in the application, taking aluminum oxide as carrier, has appropriate active ingredient, has removing impurities matter as demetalization impurity function, and to protect follow-up hydrogenation to process catalyzer, therefore protectant concept has comprised Hydrodemetalation catalyst in prior art.
In fractionation plant described in step (b), the cut-point of lighting end and last running is within the scope of 170~360 DEG C, preferably within the scope of 200~300 DEG C.
Hydrocracking reaction condition described in step (c) is: volume space velocity 0.1~1.2h when 350~445 DEG C of temperature of reaction, pressure 8.0~20.0MPa, hydrogen to oil volume ratio 500:1~5000:1 and liquid -1; The most preferred reaction conditions of hydrocracking is as follows: volume space velocity 0.2~0.8h when 375~425 DEG C of temperature of reaction, pressure 10.0~16.0MPa, hydrogen to oil volume ratio 1000:1~2000:1 and liquid -1.
Hydrocracking catalyst described in step (c) comprises cracking component and hydrogenation component, wherein cracking component is at least one in molecular sieve and 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 in Mo, W, Co and Ni, content taking oxide weight in catalyzer is 15%~40%, is preferably 25%~35%.
The weight content of cracking component in hydrocracking catalyst is generally 20%~70%, is preferably 30%~60%, and molecular sieve is generally Hydrogen Y molecular sieve, modification Hydrogen Y molecular sieve, and in amorphous aluminum silicide, the weight content of silicon-dioxide is generally 15%~55%.The pore volume of hydrocracking catalyst is generally 0.3~0.5mL/g, and specific surface area is generally 200~400m 2/ g.Hydrocracking catalyst carries out conventional sulfidizing before use, makes active ingredient be converted into sulphided state.In the inventive method, in hydrotreatment and hydrocracking process, can supplement as required appropriate sulphur or sulfocompound, in reaction process, process in the good sulphided state of activity to maintain hydrotreating catalyst and hydrocracking catalyst.
Supplement to hydrocracking reaction section reaction mass discontinuous described in step (c) NH 3, supplement NH 3in process, NH 3concentration in gaseous phase materials is 100~2000 μ g/g, is preferably 300~800 μ g/g; Supplement NH 3within 1st~100, preferably within 5th~30, carry out once for every running, carry out 1~12 hour at every turn, supplement NH 3process in hydrogen to oil volume ratio improve 200~1000 during than normal running.
After the isolated gas phase of high pressure hot separator described in step (d) is cooling, entering cold high pressure separator separates, the isolated gas phase of cold high pressure separator recycles, the isolated oil phase of cold high pressure separator enters the fractionation plant of step (b), the service temperature of high pressure hot separator is greater than 200 DEG C, and be equal to or less than hydrocracking reaction outlet material temperature, be preferably 260 DEG C 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 DEG C.The working pressure of high pressure hot separator and cold high pressure separator identical with hydrocracking reactor working pressure (ignoring the pressure-losses).
In the inventive method, hydrotreatment section and hydrocracking section can arrange respectively recycle hydrogen system, also can adopt a set of recycle hydrogen system.While adopting a set of recycle hydrogen system, the gas phase after the gas-liquid separation of hydrotreatment section reaction effluent enters hydrocracking section after imurity-removal, and the gas phase after the gas-liquid separation of hydrocracking section reaction effluent is circulated to hydrotreatment section and recycles.New hydrogen can add to hydrotreatment section, also can add to hydrocracking section.
Hydrotreating catalyst described in step (a) is adopted preparation with the following method:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that step (1) obtains mixes with the solution containing hydrogenation activity component composition, and then making beating filters, and dry, pulverize;
(3) material that step (2) obtains, moulding, then dry, roasting, obtains final Hydrobon catalyst;
Wherein step (1) carborization is prepared siliceous aluminium hydroxide and is comprised the steps:
A, by sodium aluminate solution in plastic cans, pass into containing CO simultaneously 2gas, controls pH value to 11.0~13.0, and the neutralization reaction time is 1~2 hour;
B, to add alkalescence containing silicon materials, add 2% ~ 4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained in the material of step a gained simultaneously, pass into continuously containing CO 2gas, controlling pH value is 8.0~11.0, the reaction times is 0.5~1.0 hour; Alkalescence containing silicon materials preparation method as follows: by 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, at room temperature to 70 DEG C, react and make for 0.5~48 hour, alkalescence containing silicon materials add-on by SiO in final siliceous aluminium hydroxide 2weight content is 1%~10%;
C, at the control temperature and pH value of step b, said mixture blowing air is stablized 1~3 hour;
D, the solidliquid mixture of step c gained is filtered and washed;
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 processing, and the last running obtaining enters hydrocracking section.Can avoid like this lighting end that too much scission reaction occurs, object product yield is high, and the product yields such as the dry gas of low value are low, improved whole economic efficiency.
2. hydrocracking reaction effluent carries out gas-liquid separation in high pressure hot separator, liquid phase part wherein or be all circulated to hydrotreating reactor, this flow process is different from hydrocracking reaction effluent and all enters hydrotreating reactor, and the liquid phase that is also different from hydrocracking reaction effluent all enters fractionating system and carries out fractionation processing.This flow process tool has the following advantages: avoid the light constituent in hydrocracking reaction effluent to enter hydrotreating reactor, greatly improve the hydrogen dividing potential drop in hydrotreating reactor (if light constituent enters hydrotreating reactor, light constituent can be in gas phase state, reduce the hydrogen concentration in reaction system, reduced hydrogen dividing potential drop), under the constant condition of stagnation pressure, hydrogen dividing potential drop improves the hydrogenation reaction being conducive in hydrotreating reactor, the particularly hydrogenation saturated reaction of heavy condensed-nuclei aromatics, and heavy condensed-nuclei aromatics hydrogenation saturated after, in follow-up hydrocracking reactor, be easy to carry out hydrocracking reaction, reduce coking reaction, extend the work-ing life of hydrocracking catalyst.Simultaneously, hydrocracking high pressure hot separator liquid phase enters hydrotreating reactor, can dilute coal tar raw material, reduces the wherein probability of the polymerization coking such as two rare hydrocarbon, relax the operational condition of hydrotreating reactor, be conducive to extend the work-ing life of hydrotreating catalyst.And isocrackate adopts the operating method of high pressure hot separator, also can effectively avoid macromole condensed-nuclei aromatics to separate out the problem of occluding device.
3. in hydrotreatment conversion zone of the present invention, preferably use optimized hydrotreating catalyst (referring to the application's embodiment part), this catalyzer has suitable acidity, higher hydrogenation activity, can be saturated to the effective hydrogenation of heavy condensed-nuclei aromatics, the work-ing life that is conducive to improve follow-up hydrogenation cracking catalyst.
4. by adopting flow process of the present invention and suitable hydrotreating catalyst, whole coal tar can be carried out to hydrocracking is qualified product, and the utilization ratio of coal tar improves greatly.Than adopting coking method or vacuum distillation method can improve 15 percentage points of left and right of product yield.
5. in hydrocracking reactor operating process, preferably supplement off and on appropriate NH 3.This operating method can effectively reduce hydrocracking catalyst carbon deposit, extends the work-ing life of hydrocracking catalyst.Find after deliberation, the carbon deposit major cause of hydrocracking catalyst is that condensed-nuclei aromatics is wherein adsorbed on acidity of catalyst center, constantly assembles polymerization, under hot conditions, and the hydrogenation that is not able to do in time, and there is polymerization coking reaction.In reaction process, special in the operating method of unconverted circulation, the macromole condensed-nuclei aromatics in recycle stock not section accumulation increases (under hot conditions, generating), and therefore, along with the carrying out of reaction, hydrocracking catalyst has the trend of inactivation quickening.The present invention finds by research, in coal tar hydrogenating reaction process, owing to adopting two sections of flow processs, enters impurity in hydrocracking reactor less, by the appropriate NH of regular replenishment 3, NH 3can on the acid sites of hydrocracking catalyst, form competitive adsorption with macromole condensed-nuclei aromatics, avoid macromole condensed-nuclei aromatics long-time absorption accumulation and then coking on acid sites.NH 3introducing formed competitive adsorption, can make to adsorb the macromole condensed-nuclei aromatics desorption of receiving in large acidity enters in the oil phase of reaction system, and discharge hydrocracking reactor and enter hydrotreating reactor, catalyst performance in hydrotreating reactor and reaction conditions are more suitable for the hydrogenation saturated reaction of macromole condensed-nuclei aromatics, macromolecular substance after hydrogenation is saturated is easy to occur hydrocracking reaction, and coking reaction reduces greatly.Therefore, the inventive method can effectively reduce the coking tendency of hydrocracking catalyst, extending catalyst work-ing life.At supplementary NH 3process in, suitably strengthen hydrogen-oil ratio and can effectively improve the desorption of macromole condensed-nuclei aromatics, further improve treatment effect.At supplementary NH 3process in, the cracking performance of hydrocracking catalyst slightly declines, per pass conversion only declines 1~2 percentage point, does not substantially affect normal running, and the selectivity of intermediate oil increases, the total economy of body is unaffected, stops supplementing NH 3after, reactivity worth is quick-recovery soon.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention;
In figure, 1 is coal tar raw material; 2 is hydrotreating reactor; 3 is 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.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described further:
In the inventive method, hydrotreating catalyst is most preferably adopted preparation with the following method:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that step (1) obtains mixes with the solution containing hydrogenation activity component composition, and then making beating filters, and dry, pulverize;
(3) material that step (2) obtains, moulding, then dry, roasting, obtains final Hydrobon catalyst.
Wherein step (1) carborization is prepared siliceous aluminium hydroxide and is comprised the steps:
A, by sodium aluminate solution in plastic cans, pass into containing CO simultaneously 2gas, controls pH value to 11.0~13.0, and the neutralization reaction time is 1~2 hour;
B, to add alkalescence containing silicon materials, add 2% ~ 4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained in the material of step a gained simultaneously, pass into continuously containing CO 2gas, controlling pH value is 8.0~11.0, the reaction times is 0.5~1.0 hour; Alkalescence containing silicon materials preparation method as follows: by 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, at room temperature to 70 DEG C, react and make for 0.5~48 hour, alkalescence containing silicon materials add-on by SiO in final siliceous aluminium hydroxide 2weight content is 1%~10%;
C, at the control temperature and pH value of step b, said mixture blowing air is stablized 1~3 hour;
D, the solidliquid mixture of step c gained is filtered and washed;
The solids drying of e, steps d gained obtains siliceous aluminium hydroxide.
The above-mentioned carborization of the present invention is prepared in siliceous aluminium hydroxide process, and it is 20 ~ 40 DEG C that step a and step b control temperature of reaction; In step a, the concentration of sodium aluminate solution used is 15 ~ 60gAl 2o 3/ L, is preferably 20 ~ 40gAl 2o 3/ L; Containing CO 2the volumetric concentration of gas is 10v% ~ 50v%; Polymeric surface active agent described in step b is one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether, fatty alkanol amide and polyacrylamide, and the molecular weight of above-mentioned polymeric surface active agent is 1.8~2.3 ten thousand; Washing described in step c is to be washed till neutrality with the deionized water of 40 ~ 90 DEG C; Drying conditions described in step e is to be dried 4 ~ 10 hours at 110 ~ 130 DEG C; The pH value that step a controls reaction end is 11.5~12.0, and it is 10.0~11.0 that step b controls pH value constant; It is lower by 0.3 ~ 4.0 than the pH value of step a control reaction end that step b controls constant pH value, is preferably low by 1.0 ~ 2.0.
Coal tar hydrogenating of the present invention is processed in method for preparing catalyst step (2), be the solution containing W, Mo, Ni and at least one compound of Co containing the solution of hydrogenation activity component composition, as ammonium metawolframate, ammonium molybdate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES etc., being dried as at 60 ~ 200 DEG C dry 1 ~ 8 hour wherein.
In hydrotreating catalyst preparation method step of the present invention (3), moulding process can add suitable auxiliary agent on demand, as peptizing agent, extrusion aid, expanding agent etc., peptizing agent, expanding agent, extrusion aid etc. can be materials conventional in this area, if peptizing agent is nitric acid or acetic acid, expanding agent is carbon black, tensio-active agent, starch etc., extrusion aid powder as blue or green in field etc.Drying process be wherein generally 80 ~ 200 DEG C dry 1 ~ 10 hour, roasting is roasting 1 ~ 5 hour at 350 ~ 500 DEG C.
In hydrotreating catalyst preparation method of the present invention, can add required suitable auxiliary agent at step (1), (2) to the arbitrary steps of (3).
Coal tar hydrogenating of the present invention is processed in method for preparing catalyst, and other technology contents is well known to those skilled in the art, as the preparation of solution, and dry method, the equipment of roasting etc.
Coal tar hydrogenating of the present invention is processed catalyzer taking silicon-containing alumina as carrier, and taking VIB and VIII metallic element as active ingredient, taking oxide compound, the weight content in catalyzer is 25% ~ 60% to active ingredient, 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 catalyzer, can contain suitable auxiliary agent, and as Zr, Ti, P etc., auxiliary agent can add in solid support material preparation process, also can in catalyst preparation process, add, and auxiliary agent content is 1% ~ 15%.Coal tar hydrogenating of the present invention is processed in catalyzer, and active ingredient is one or more in W, Mo, Ni, Co, preferred following combination: Mo-Ni, Mo-Co-Ni, W-Mo-Co-Ni.Coal tar hydrogenating of the present invention is processed in 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 catalyzer, adopting siliceous is carrier containing changing aluminium, the siliceous aluminium hydroxide that adopts suitable carborization to prepare is carrier precursor, and hydrogenation activity that can obvious bright high catalyst, particularly to the saturated performance of the hydrogenation of macromole condensed-nuclei aromatics.In this siliceous aluminium hydroxide preparation process, add specific alkalescence containing silicon materials, can improve the acidity of final catalyzer, and then the hydrogenation and removing reaction to itrogenous organic substance while improving Hydrobon catalyst reconstructed coal tar.Alkalescence is that high alkalinity, suitable silica alumina ratio material obtain after suitable reaction containing silicon materials, and the process that this alkalescence is prepared silicon-containing alumina containing silicon materials with carborization combines, and 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 active metal, during simultaneously due to siliceous aluminium hydroxide shaping and roasting after dipping active ingredient, do not affect the formation of pore volume and specific surface, therefore, in hydrotreating catalyst prepared by the inventive method, under the higher prerequisite of active component content, still there is larger pore volume and specific surface area.
Further illustrate 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: coal tar raw material and hydrogen enter hydrotreating reactor 2 and carries out that hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation, rare hydrocarbon are saturated etc. reacts.Hydrotreatment reaction effluent after gas-liquid separation, gas phase after imurity-removal for hydrocracking reaction; Liquid phase enters 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.Hydrocracking reaction effluent is separated into liquid and gas in high pressure hot separator 9, and liquid phase circulation returns hydrotreating reactor, after gas phase is cooling, enters cold high pressure separator 10, and gas phase recycles, and oil phase enters separation column 4 and carries out fractionation.
Table 1 is destructive distillation coal tar main character, and table 3 is product main character of the present invention.
Embodiment 1
The low-temperature pyrolysis coal tar of Yilan brown coal, character is in table 1, send to after pretreatment unit removes mechanical impurity and water and enter atmospheric fractional tower, fractionate out oil and carbolic oil (carbolic oil of lateral line withdrawal function) at the bottom of benzoline (overhead oil), tower, carbolic oil enters carbolic oil extraction plant and isolates phenol products and dephenolize oil.At the bottom of dephenolize oil, benzoline tower, after oil mixing, enter hydrotreater and carry out hydrotreatment reaction, the gasoline fraction and the diesel oil distillate that obtain are reacted in hydrotreatment can go out device, hydrotreatment is reacted the heavy distillate that obtains (between heavy distillate and diesel oil by 325 DEG C of cuttings) and is entered hydroeracking unit and carry out hydrocracking reaction, hydrocracking reaction product is separated into gas phase and liquid phase in high pressure hot separator, and liquid phase circulation returns hydrotreater.Gas phase enters cold high score and separates the gas phase obtaining and loop back hydrotreater, and oil phase enters the separation column of hydrotreatment reaction product.Volume space velocity 0.64h when the temperature of reaction of hydrotreatment is 325 DEG C, pressure 15.1MPa, hydrogen to oil volume ratio 1000:1 and liquid -1; Volume space velocity 0.3h when 372 DEG C of the temperature of reaction of hydrocracking, pressure 15.9MPa, hydrogen to oil volume ratio 1200:1 and liquid -1.Hydrotreating catalyst is conventional hydrotreating catalyst, and with alumina supporter, molybdenum oxide weight content is 15%, and Tungsten oxide 99.999 weight content is 12%, and nickel oxide weight content is 5%, and specific surface area is 185m 2/ g, pore volume is 0.35ml/g.Hydrocracking catalyst is conventional hydrocracking catalyst, (silica/alumina molecular ratio is as 12 taking Y zeolite for catalyzer, structure cell is often for 0.2426nm) and amorphous aluminum silicide (silica weight content is 27%, infrared acidity is 0.4mmol/g) be cracking component, Y zeolite weight content is 15%, amorphous aluminum silicide weight content is 35%, Tungsten oxide 99.999 weight content is 28%, nickel oxide weight content is 8%, and surplus is aluminum oxide, and specific surface area is 270m 2/ g, pore volume is 0.42ml/g.Hydrotreating catalyst and hydrocracking catalyst carry out conventional prevulcanized processing before use.Turn round after 3000 hours, maintain identical transformation efficiency (it is 55% control that transformation efficiency is less than 325 DEG C of distillate weight yields by hydrocracking reactor outlet, lower same) and need 10 DEG C of temperature raisings.
Embodiment 2
Prepare hydrotreating catalyst (in oxide weight) by following composition: Mo, 30.0%; W, 8.0%; Ni, 2.5%; Co, 2.0%.
Be the solution containing ammonium metawolframate, ammonium molybdate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES containing the solution of active ingredient; 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 to concentration 2o 3the dense sodium aluminate solution of/L, it is 25gAl that redilution becomes concentration 2o 3/ L sodium aluminate working solution first adds 10L to contain 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 DEG C of temperature of reaction, the reaction times is 1 hour, pH value is reacted at 12.0 o'clock, by adding alkalescence containing silicon materials containing silica weight 5% in final silyl hydride aluminium, adding simultaneously and adding molecular weight by siliceous aluminium hydroxide weight 3% is 20,000 polyoxyethylene glycol, passes into continuously containing CO 2gas, makes the pH of system remain on 10.5 left and right, 25 DEG C of temperature of reaction, and the reaction times is 1 hour, after question response is complete, stops passing into CO 2, then blowing air is stablized 60 minutes, and slurries filter and use 60 DEG C of deionized waters to be washed till neutrality.Then be dried 8 hours at 120 DEG C, obtain siliceous aluminium hydroxide Y-1.
Siliceous material preparation method is as follows for its neutral and alkali: by 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, reacts and make for 12 hours at 45 DEG C.
(2) catalyzer preparation.Siliceous hydroxide Y-1 adds the solution impregnation said mixture material containing hydrogenation activity component, then at 120 DEG C, be dried 2 hours, add appropriate peptizing agent, account for the blue or green powder in field of siliceous aluminium hydroxide weight 2%, kneading becomes plastic, then extruded moulding, and stripe shape thing is dried 5 hours at 120 DEG C, 450 DEG C 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 it is hydrotreating catalyst that hydrotreatment section is used C-1.
Embodiment 3
Raw material is certain mixed coal tar, and main character is in table 2.Hydrotreatment section temperature of reaction is 350 DEG C, before hydrotreatment section, uses hydrogenation protecting agent to carry out pre-treatment, and hydrogenation protecting agent is conventional hydrogenation protecting agent, and taking aluminum oxide as carrier, containing molybdenum oxide 6%, cobalt oxide 1%, pore volume is 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 while being 310 DEG C, pressure 15.1MPa, hydrogen to oil volume ratio 1200:1 and liquid -1.Other is identical with embodiment 2.
Embodiment 4
Press the method for embodiment 3, scheme one: every running 8 days, hydrocracking reactor supplements 2 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 350 μ g/g, after 1500 hours, maintains identical transformation efficiency and needs 3 DEG C of temperature raisings.Turn round after 3000 hours, maintain identical transformation efficiency and need 2 DEG C of temperature raisings again.Scheme two: every running 25 days, hydrocracking reactor supplements 5 hours ammonia, and the concentration of ammonia gas phase under reaction conditions is 750 μ g/g, and the hydrogen to oil volume ratio that increases hydrocracking reactor when mending ammonia is to 1700:1, after 1500 hours, maintain identical transformation efficiency and need 4 DEG C of temperature raisings.Turn round after 3000 hours, maintain identical transformation efficiency and need 3 DEG C of temperature raisings again.
Comparative example 1
Press the method for embodiment 1, hydrocracking reaction effluent all enters hydrotreating reactor.Turn round after 3000 hours, maintain identical transformation efficiency and need 25 DEG C of temperature raisings.
Comparative example 2
Press the method for embodiment 4, hydrocracking reactor is not mended ammonia operation, turns round after 1500 hours, and while maintaining identical transformation efficiency, temperature of reaction need promote 8 DEG C.Turn round after 3000 hours, maintain identical transformation efficiency and need 13 DEG C of temperature raisings again.
Table 1 destructive distillation coal tar main character
Raw material Middle coalite tar
Density (20 DEG C), g/cm 3 ??0.9812
Boiling range, DEG C
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/DEG C ??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
Product main character Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4*
Petroleum naphtha
Nitrogen content, μ gg -1 ??<0.5 ??<0.5 ??<0.5 ??<0.5
Sulphur content, μ gg -1 ??<0.5 ??<0.5 ??<0.5 ??<0.5
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 ??44.2 ??45.3 ??41.5 ??41.4
* result after turning round 3000 hours by scheme two.

Claims (9)

1. a coal tar two-stage hydrogenation processing method, is characterized in that comprising the steps:
(a) coal tar raw material enters hydrotreatment conversion zone, exists and contacts with hydrotreating catalyst under hydroprocessing condition at hydrogen, carries out hydrotreatment reaction;
(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 step (b) obtains enters hydrocracking reaction section, exists and contacts with hydrocracking catalyst under hydrocracking condition at hydrogen, carries 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 hydrotreatment conversion zone of step (a);
Wherein, in 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 entering before hydrogenation unit, and pretreatment process comprises one or more in dehydration, desalination and de-solid impurity;
Hydrotreating catalyst described in step (a) is adopted preparation with the following method:
(1) adopt carborization to prepare siliceous aluminium hydroxide;
(2) the siliceous aluminium hydroxide that step (1) obtains mixes with the solution containing hydrogenation activity component composition, and then making beating filters, and dry, pulverize;
(3) material that step (2) obtains, moulding, then dry, roasting, obtains final hydrotreating catalyst;
Wherein step (1) carborization is prepared siliceous aluminium hydroxide and is comprised the steps:
A, sodium aluminate solution is poured in plastic cans, passed into containing CO simultaneously 2gas, controls pH value to 11.0~13.0, and the neutralization reaction time is 1~2 hour;
B, to add alkalescence containing silicon materials, add 2%~4% the polymeric surface active agent that accounts for the siliceous aluminium hydroxide weight of step e gained in the material of step a gained simultaneously, pass into continuously containing CO 2gas, controlling pH value is 8.0~11.0, the reaction times is 0.5~1.0 hour; Alkalescence containing silicon materials preparation method as follows: by 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, at room temperature to 70 DEG C, react and make for 0.5~48 hour, alkalescence containing silicon materials add-on by SiO in final siliceous aluminium hydroxide 2weight content is 1%~10%;
C, at the control temperature and pH value of step b, said mixture blowing air is stablized 1~3 hour;
D, the solidliquid mixture of step c gained is filtered and washed;
The solids drying of e, steps d gained obtains siliceous aluminium hydroxide.
2. processing method according to claim 1, is characterized in that: the hydroprocessing condition described in step (a) is: volume space velocity 0.1~1.5h when 180~435 DEG C of temperature of reaction, pressure 8.0~20.0MPa, hydrogen to oil volume ratio 300:1~5000:1 and liquid -1.
3. processing method according to claim 1, it is characterized in that: the hydrotreating catalyst described in step (a) is taking aluminum oxide as carrier, taking one or more in Mo, W, Co and Ni as active ingredient, hydrotreating catalyst vulcanized before using, and made active ingredient be converted into sulphided state; In hydrotreating catalyst taking the active component content of oxide weight as 5%~55%.
4. processing method according to claim 1; it is characterized in that: the coal tar raw material described in step (a) contacted with protective material before hydrotreatment; protective material consumption is 10%~100% of hydrotreating catalyst volume; protectant active ingredient is one or more in Mo, W, Co and Ni; active ingredient is taking the content of oxide weight as 0~20%; protective material pore volume is 0.4~1.5mL/g, and specific surface area is 20~200m 2/ g.
5. processing method according to claim 1, is characterized in that: in the fractionation plant described in step (b), the cut-point of lighting end and last running is within the scope of 170~360 DEG C.
6. processing method according to claim 1, is characterized in that: the hydrocracking reaction condition described in step (c) is: volume space velocity 0.1~1.2h when 350~445 DEG C of temperature of reaction, pressure 8.0~20.0MPa, hydrogen to oil volume ratio 500:1~5000:1 and liquid -1.
7. processing method according to claim 1, it is characterized in that: the hydrocracking catalyst described in step (c) comprises cracking component and hydrogenation component, wherein cracking component is at least one in molecular sieve and amorphous aluminum silicide, the weight content of cracking component in hydrocracking catalyst is 20%~70%, hydrogenation component is one or more in Mo, W, Co and Ni, and the content taking oxide weight in catalyzer is 15%~40%.
8. processing method according to claim 1, is characterized in that: supplement to the hydrocracking reaction section reaction mass discontinuous described in step (c) NH 3, supplement NH 3in process, NH 3concentration in gaseous phase materials is 100~2000 μ g/g, supplements NH 3for every 1~100 day running once, carry out 1~12 hour at every turn, supplement NH 3process in hydrogen to oil volume ratio improve 200~1000 during than normal running.
9. processing method according to claim 1, it is characterized in that: after the isolated gas phase of high pressure hot separator described in step (d) is cooling, enter cold high pressure separator and separate, the isolated gas phase of cold high pressure separator recycles, the isolated oil phase of cold high pressure separator enters the fractionation plant of step (b), the service temperature of high pressure hot separator is greater than 200 DEG C, and will be equal to or less than hydrocracking reaction outlet material temperature.
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Publication number Priority date Publication date Assignee Title
US20150141726A1 (en) * 2013-11-19 2015-05-21 Uop Llc Process for producing olefins from a coal feed
CN103695031B (en) * 2013-12-27 2015-07-22 成都博晟能源科技有限公司 Method for producing diesel oil and bunker fuel blend component from coal tar
CN105238440B (en) * 2014-07-07 2018-05-04 江苏湖大化工科技有限公司 A kind of middle coalite tar method of hydrotreating
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597093A (en) * 2003-09-15 2005-03-23 中国石油化工股份有限公司 Method of preparing amorphous silica-alumina using carbonization
CN1952071A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 Combined method for producing cleaning oil from coal-tar oil
CN1952070A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 Method for producing cleaning oil from coal-tar oil
CN101240193A (en) * 2007-02-09 2008-08-13 中国石油化工股份有限公司 Coal tar multistage hydrogenation treatment technique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597093A (en) * 2003-09-15 2005-03-23 中国石油化工股份有限公司 Method of preparing amorphous silica-alumina using carbonization
CN1952071A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 Combined method for producing cleaning oil from coal-tar oil
CN1952070A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 Method for producing cleaning oil from coal-tar oil
CN101240193A (en) * 2007-02-09 2008-08-13 中国石油化工股份有限公司 Coal tar multistage hydrogenation treatment technique

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