CN103433053B - A kind of coal tar hydrogenating produces process and the catalyst of diesel oil - Google Patents
A kind of coal tar hydrogenating produces process and the catalyst of diesel oil Download PDFInfo
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Abstract
The invention provides a kind of coal tar hydrogenating and produce the process that diesel oil catalyst and coal tar hydrogenating produce diesel oil.Coal tar hydrogenating of the present invention produces diesel oil catalyst, comprises catalyst for hydro-upgrading and hydrocracking catalyst; Described catalyst for hydro-upgrading comprises: molybdenum oxide, cobalt oxide, nickel oxide and alumina catalyst support; Described hydrocracking catalyst comprises: tungsten oxide, cobalt oxide, nickel oxide and alumina catalyst support.Catalyst of the present invention is using activated alumina as the carrier of catalyst, make the expanded range can carrying out the coal tar processed, use two-stage hydrogenation catalyst simultaneously, be conducive to reducing the arene content in diesel oil distillate, also oil density can be reduced, improve Cetane number, make product reach the instructions for use of fuel oil engine.<pb pnum="1" />
Description
Technical field
The present invention relates to kerosene chemical technology field, particularly relate to process and catalyst that a kind of coal tar hydrogenating produces diesel oil.
Background technology
Coal tar is the important byproduct of in coal thermal cracking distillation process process, and it is based on aromatic hydrocarbon, and sulphur, nitrogen, oxygen content are high, the complex mixture that C/Hratio is large.According to the difference of coal thermal cracking pyrolysis temperature and process approach, coal tar can be divided into coalite tar, medium temperature coal tar and high temperature coal-tar.
Along with the continuous increase of coal tar output, clean processing and effective utilization of coal tar are more and more important.Current high temperature coal-tar processing method isolates various chemicals by distillation, crystallization and the technique such as refining, and with it for raw material carries out deep processing.And be obtain primary fuel by techniques such as simple fore-running, pickling, alkali cleaning, refining and allotments for the processing of coalite tar, the quality of this product is not high, and added value is also very little.Through years of researches, it is found that coal tar hydrogenating technology can produce the clean fuel oil of high-quality, therefore coal tar hydrogenating technology have received and pays close attention to widely.
Coal tar hydrogenating clean fuel oil just has research as far back as eighties of last century three, the forties, but due to reaction pressure very high, all do not realize industrialization; Until eighties of last century the eighties Japan have developed this technology.The technique of existing coal tar hydrogenating diesel oil distillate comprises the process such as distillation, hydrogenation reaction, separation, fractionation of coal tar; Component and the ratio of hydrogenation used catalyst are incomplete same, but are substantially all adopt molybdenum, nickel, tungsten, cobalt etc. as hydrogenation active component.Owing to containing a large amount of sulphur in coal tar, the hetero atom such as nitrogen and oxygen and polycyclic aromatic hydrocarbon, colloid and asphalitine, its cracking performance is poor, and easy polycondensation under high-temperature hydrogenation reaction condition, the large molecule coke generated makes the active component inactivation of conventional hydrogenation catalyst, reaction system coking, therefore the engine fuel adopting conventional hydrogen addition technology reconstructed coal tar to carry out production lightweight will there will be reaction system coke deposition, the problem such as catalyst service life is short, namely this kind of catalyst is suitable for processing coalite tar, but be not suitable for the high temperature tar that process asphaltenes is more, the life-span of catalyst also greatly reduces than in PETROLEUM PROCESSING, general at about 1 year, the product Cetane number of simultaneously producing is also lower, the instructions for use of fuel oil engine can not be reached completely.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of coal tar hydrogenating diesel oil catalyst, and catalyst provided by the invention is applicable to high/low temperature coal tar, and the diesel oil produced meets the instructions for use of fuel material engine.
In view of this, the invention provides a kind of coal tar hydrogenating and produce diesel oil catalyst, comprise catalyst for hydro-upgrading and hydrocracking catalyst,
Described catalyst for hydro-upgrading, comprising: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
Described hydrocracking catalyst, comprising: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus.
Preferably, the granularity of activated alumina described in described catalyst for hydro-upgrading is 40nm ~ 50nm; The granularity of activated alumina described in described hydrocracking catalyst is 40nm ~ 50nm.
Preferably, the specific area of described catalyst for hydro-upgrading is 180m
2/ g ~ 250m
2/ g, pore volume is 0.5ml/g ~ 0.8ml/g.
Preferably, the specific area of described hydrocracking catalyst is 180m
2/ g ~ 250m
2/ g, pore volume is 0.6ml/g ~ 0.8ml/g.
Present invention also offers the process that a kind of coal tar hydrogenating produces diesel oil distillate, comprise the following steps:
The cut of less than 360 DEG C will be cut after coal tar air-distillation;
The cut of less than 360 DEG C is carried out hydro-upgrading reaction and hydrocracking reaction successively;
The catalyst of described hydro-upgrading reaction comprises: comprising: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
The catalyst of described hydrocracking reaction comprises: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
Product after hydrocracking is carried out fractionation again after high-low pressure separation, obtain diesel oil distillate.
Preferably, the temperature of described hydro-upgrading reaction is 350 DEG C ~ 380 DEG C, and pressure is 10.0MPa ~ 16.0MPa, and hydrogen to oil volume ratio is (800 ~ 1000): 1, and air speed is 0.8h
-1~ 1.0h
-1.
Preferably, the temperature of described hydrocracking reaction is 350 DEG C ~ 400 DEG C, and pressure is 15.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is (900 ~ 1100): 1, and air speed is 1.0h
-1~ 1.2h
-1.
Preferably, the specific area of the catalyst of described hydro-upgrading reaction is 180m
2/ g ~ 250m
2/ g, pore volume is 0.5ml/g ~ 0.8ml/g.
Preferably, the specific area of the catalyst of described hydrocracking reaction is 180m
2/ g ~ 250m
2/ g, pore volume is 0.6ml/g ~ 0.8ml/g.
Preferably, described in the catalyst of described hydro-upgrading reaction, the granularity of activated alumina is 40nm ~ 50nm; The granularity of activated alumina described in the catalyst of described hydrocracking reaction is 40nm ~ 50nm.
The invention provides a kind of coal tar hydrogenating diesel oil catalyst, described catalyst comprises: catalyst for hydro-upgrading and hydrocracking catalyst.Described catalyst for hydro-upgrading is using molybdenum oxide, cobalt oxide and nickel oxide as main catalyst component, hydrogenation sites is provided, activated alumina is as co-catalyst or carrier, and the effect of catalyst for hydro-upgrading is the carrying out promoting desulfurization removing nitric, the sulphur nitrogen component in coal tar is removed; Described hydrocracking catalyst, using tungsten oxide, cobalt oxide and nickel oxide as main catalyst component, provides the activated centre of hydrogenation, and activated alumina is as co-catalyst or carrier, and hydrocracking catalyst plays hydrogenation open loop cracking.Catalyst of the present invention is using activated alumina as the carrier of catalyst, make the expanded range can carrying out the coal tar processed, use two-stage hydrogenation catalyst simultaneously, be conducive to reducing the arene content in diesel oil distillate, also oil density can be reduced, improve Cetane number, make product reach the instructions for use of fuel oil engine.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of coal tar hydrogenating diesel oil distillate catalyst, comprise catalyst for hydro-upgrading and hydrocracking catalyst, described catalyst for hydro-upgrading, comprise: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
Described hydrocracking catalyst, comprising: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus.
According to the present invention, molybdenum oxide in the catalyst for hydro-upgrading of catalyst of the present invention, cobalt oxide and nickel oxide are as main catalyst component, for hydrogenation desulfurization and denitrogenation provides the activated centre of reaction, and activated alumina is as co-catalyst or carrier, coordinate the carrying out of major catalyst catalytic desulfurhydrogenation denitrification reaction.Activated alumina is also known as activated bauxite, and it is the solid material of a kind of porous, high degree of dispersion, and surface area is comparatively large, and its micropore surface possesses absorption property, surface-active and excellent heat endurance etc.The granularity of activated alumina of the present invention is preferably 40 ~ 50nm.The specific area of described catalyst for hydro-upgrading is 180m
2/ g ~ 250m
2/ g, pore volume is preferably 0.5ml/g ~ 0.8ml/g; For the catalyst of same quality, granularity and pore volume less, specific surface area of catalyst is larger, and activated centre and the contact raw area of catalyst are also more, and catalytic action is also just more remarkable, and the effect for catalyst for hydro-upgrading then desulfurization removing nitric is better.The preparation method of the present invention to described activated alumina has no particular limits, and preferably adopts the method preparation of collosol and gel.
Catalyst for hydro-upgrading of the present invention has the catalytic action of desulfurization removing nitric.Described catalyst for hydro-upgrading comprises the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus; The content of described molybdenum oxide is preferably 4.5wt% ~ 7.5wt%, and the content of described cobalt oxide is preferably 3wt% ~ 5wt%, and the content of described nickel oxide is preferably 3.5wt% ~ 8wt%.
Also comprise hydrocracking catalyst in catalyst of the present invention, described hydrocracking catalyst is the catalyst of hydrogenation open loop and cracking.Hydrocracking catalyst of the present invention equally with tungsten oxide, cobalt oxide and nickel oxide for main catalyst component, for hydrogenation open loop cracking provides the activated centre of reaction, and activated alumina is as co-catalyst or carrier, coordinate the carrying out of major catalyst catalytic hydrogenation open loop and cracking reaction.The granularity of activated alumina of the present invention is preferably 40 ~ 50nm, and the specific area of described catalyst for hydro-upgrading is 180m
2/ g ~ 250m
2/ g, pore volume is preferably 0.6ml/g ~ 0.8ml/g.For the catalyst of same quality, granularity and pore volume less, specific surface area of catalyst is larger, and activated centre and the contact raw area of catalyst are also more, catalytic action is also just more remarkable, and the effect for hydrocracking catalyst then hydrogenation open loop cracking is better.The preparation method of the present invention to described activated alumina has no particular limits, and preferably adopts sol-gal process preparation.
Hydrocracking catalyst of the present invention comprises the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus.The content of described tungsten oxide is preferably 4.5wt% ~ 8.5wt%, is more preferably 5.5wt% ~ 7wt%, and the content of described cobalt oxide is preferably 3.5wt% ~ 5.5wt%, and the content of described nickel oxide is preferably 3.5wt% ~ 8wt%, is more preferably 4.5wt% ~ 7.5wt%.
The preparation method of catalyst for hydro-upgrading of the present invention and hydrocracking catalyst has no particular limits, and preferably adopts infusion process preparation.When preparing catalyst for hydro-upgrading, aluminium oxide be impregnated in the solution of molybdenum oxide, cobalt oxide and nickel oxide, after dipping balance, by the removing of remaining liquid, then carrying out drying, roasting and activation etc., can catalyst for hydro-upgrading be obtained.The preparation method of same described hydrocracking catalyst is: be impregnated in by aluminium oxide in the solution of tungsten oxide, cobalt oxide and nickel oxide, after dipping balance, by the removing of remaining liquid, then carries out drying, roasting and activation, can obtain hydrocracking catalyst.
Present invention also offers the process that coal tar hydrogenating produces diesel oil, comprise the following steps:
The cut of less than 360 DEG C will be cut after coal tar air-distillation;
The cut of less than 360 DEG C is carried out hydro-upgrading reaction and hydrocracking reaction successively;
The catalyst of described hydro-upgrading reaction comprises: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
The catalyst of described hydrocracking reaction comprises: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus;
Product after hydrocracking is carried out fractionation again after high-low pressure separation, obtain diesel oil distillate.
According to the present invention, produce in the process of diesel oil at coal tar hydrogenating, first by coal tar atmospheric and vacuum distillation, cut the diesel oil distillate being wherein less than 360 °; The atmospheric and vacuum distillation of the diesel oil of coal described in the present invention is technological means well known to those skilled in the art, and the present invention has no particular limits.
Then the diesel oil distillate of less than 360 ° is carried out hydro-upgrading reaction and hydrocracking reaction successively.Described hydro-upgrading reaction mainly plays desulfurization removing nitric, and wherein desulfurization is, by hydrogenation reaction, the sulphidic conversion in coal tar is become hydrocarbon and hydrogen sulfide, and denitrogenation is, by hydrogenation reaction, the nitrogen compound in coal tar is changed into hydrocarbon and ammonia.In described hydro-upgrading course of reaction, the temperature of described reaction is preferably 350 DEG C ~ 380 DEG C, and pressure is preferably 10.0MPa ~ 16.0MPa, and hydrogen to oil volume ratio is preferably (800 ~ 1000): 1, and air speed is preferably 0.8h
-1~ 1.0h
-1.And the catalyst of described hydro-upgrading reaction comprises: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus.In the process that described hydro-upgrading reacts, by cooperatively interacting of catalyst and reaction condition, the desulfurization removing nitric of coal tar is carried out fully and completely.
According to the present invention, after the diesel oil distillate of described less than 360 ° carries out hydro-upgrading process, then carry out hydrocracking reaction.Described hydrocracking is in petroleum refining process at elevated pressures temperature, and hydrogen makes mink cell focus generation hydrogenation, cracking and isomerization reaction through catalyst action, is converted into the process of light oil.Hydrocracking is in fact the combination of hydrogenation and catalytic cracking process, heavy oil product can be made to generate the light-end products such as gasoline, diesel oil and kerosene by catalytic cracking reaction, can prevent from again generating a large amount of coke, by impurity removals such as the sulphur in crude oil, nitrogen, oxygen, and olefin saturated can also be made.Hydrocracking reaction described in the present invention makes condensed-nuclei aromatics open loop hydrocracking.In described hydrocracking reaction process, the temperature of described reaction is preferably 350 DEG C ~ 400 DEG C, and pressure is preferably 15.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is preferably (900 ~ 1100): 1, and air speed is preferably 1.0h
-1~ 1.2h
-1.The catalyst of described hydrocracking reaction comprises simultaneously: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus.In the process of described hydrocracking, the present invention is cooperatively interacted by catalyst and reaction condition, makes the process of hydrocracking more thorough, improves the yield of light oil distillate.
Product after hydrocracking carries out fractionation after carrying out high-low pressure separation according to mode well known to those skilled in the art again, namely obtains diesel oil distillate.
The present invention produces in the process of diesel oil distillate at coal tar hydrogenating, catalyst is added respectively in the process of hydro-upgrading and hydrocracking, catalyst is using activated alumina as carrier, improve coal tar hydrogenation catalyst desulfurization removing nitric and open loop cracking performance respectively, make the expanded range of available coal tar, use two-stage hydrogenation can more be conducive to reducing the arene content in diesel oil distillate, also can reduce oil density, improve Cetane number, make product reach the instructions for use of fuel oil engine.
Produce to coal tar hydrogenating provided by the invention the process that diesel oil catalyst and coal tar hydrogenating produce diesel oil to be described in detail, protection scope of the present invention is not limited by the following examples.
Raw material of the present invention is commercially available prod.
Embodiment 1
Coal tar hydrogenating diesel oil distillate catalyst, comprise catalyst for hydro-upgrading and hydrocracking catalyst, wherein said catalyst for hydro-upgrading comprises by weight percentage: molybdenum oxide 4%, cobalt oxide 6%, nickel oxide 7%, all the other granularities are the activated alumina of 50nm; Activated alumina be impregnated in the solution of molybdenum oxide, cobalt oxide and nickel oxide, after dipping 12h, the mixed liquor obtained is carried out drying, roasting and activation successively, obtains catalyst for hydro-upgrading.The specific area of described catalyst for hydro-upgrading is 250m
2/ g, pore volume is 0.8ml/g; Described hydrocracking catalyst comprises by weight percentage: tungsten oxide 5%, cobalt oxide 4%, nickel oxide 6%, all the other for granularity be the activated alumina of 50nm; Activated alumina be impregnated in the solution of tungsten oxide, cobalt oxide and nickel oxide, after dipping 12h, the mixed liquor obtained is carried out drying, roasting and activation successively, obtains hydrocracking catalyst.The specific area of described hydrocracking catalyst is 250m
2/ g, pore volume is 0.6ml/g.
Embodiment 2
The preparation method of catalyst for hydro-upgrading is identical with the preparation method of catalyst for hydro-upgrading described in embodiment 1, and difference is: described catalyst for hydro-upgrading comprises: molybdenum oxide 8%, cobalt oxide 3%, nickel oxide 4%, all the other for granularity be the activated alumina of 50nm; The specific area of described catalyst for hydro-upgrading is 250m
2/ g, pore volume is 0.75ml/g;
The preparation method of hydrocracking catalyst is identical with the preparation method of hydrocracking catalyst described in embodiment 1, and difference is: described hydrocracking catalyst comprises: tungsten oxide 8%, cobalt oxide 2%, nickel oxide 3%, all the other for granularity be the activated alumina of 50nm; The specific area of described hydrocracking catalyst is 220m
2/ g, pore volume is 0.6ml/g.
Embodiment 3
The preparation method of catalyst for hydro-upgrading is identical with the preparation method of catalyst for hydro-upgrading described in embodiment 1, and difference is: described catalyst for hydro-upgrading comprises: molybdenum oxide 6%, cobalt oxide 4%, nickel oxide 5%, all the other for granularity be the activated alumina of 50nm; The specific area of described catalyst for hydro-upgrading is 220m
2/ g, pore volume is 0.8ml/g;
The preparation method of hydrocracking catalyst is identical with the preparation method of hydrocracking catalyst described in embodiment 1, and difference is: tungsten oxide 7%, cobalt oxide 3%, nickel oxide 6%, all the other for granularity be the activated alumina of 50nm; The specific area of described hydrocracking catalyst is 250m
2/ g, pore volume is 0.7ml/g.
Embodiment 4
The cut being less than 360 DEG C is cut by after coal tar Atmospheric vacuum pre-distillation; Described cut is carried out hydro-upgrading reaction in the first reactor, the catalyst for hydro-upgrading that catalyst used adopts embodiment 1 to prepare, reaction temperature is 360 DEG C, and reaction pressure is 15.0MPa, and the volume ratio of hydrogen oil is 800:1, and during liquid, volume space velocity is 1.0h
-1; Feedstock oil after upgrading enters in hydrocracking reactor and carries out hydrocracking reaction, the hydrocracking catalyst that catalyst used adopts embodiment 1 to prepare, reaction temperature is 380 DEG C, and pressure is 17.0MPa, the volume ratio of hydrogen oil is 1000:1, and during liquid, volume space velocity is 1.2h
-1; Hydrocracking reaction afterproduct enters fractionating column again and cuts diesel oil distillate after high-low pressure separator is separated.The diesel oil distillate prepared by the present embodiment detects, and the character of diesel oil distillate is as shown in table 1.
Embodiment 5
The cut being less than 360 DEG C is cut by after coal tar Atmospheric vacuum pre-distillation; Described cut is carried out hydro-upgrading reaction in the first reactor, the catalyst for hydro-upgrading that catalyst used adopts embodiment 2 to prepare, reaction temperature is 350 DEG C, and reaction pressure is 16.0MPa, and the volume ratio of hydrogen oil is 800:1, and during liquid, volume space velocity is 1.0h
-1; Feedstock oil after upgrading enters in hydrocracking reactor and carries out hydrocracking reaction, the hydrocracking catalyst that catalyst used adopts embodiment 2 to prepare, reaction temperature is 380 DEG C, and pressure is 17.0MPa, the volume ratio of hydrogen oil is 900:1, and during liquid, volume space velocity is 1.2h
-1; Hydrocracking reaction afterproduct enters fractionating column again and cuts diesel oil distillate after high-low pressure separator is separated.The diesel oil distillate prepared by the present embodiment detects, and the character of diesel oil distillate is as shown in table 1.
Embodiment 6
The cut being less than 360 DEG C is cut by after coal tar Atmospheric vacuum pre-distillation; Described cut is carried out hydro-upgrading reaction in the first reactor, the catalyst for hydro-upgrading that catalyst used adopts embodiment 3 to prepare, reaction temperature is 360 DEG C, and reaction pressure is 15.0MPa, and the volume ratio of hydrogen oil is 900:1, and during liquid, volume space velocity is 1.0h
-1; Feedstock oil after upgrading enters in hydrocracking reactor and carries out hydrocracking reaction, the hydrocracking catalyst that catalyst used adopts embodiment 3 to prepare, reaction temperature is 390 DEG C, and pressure is 17.0MPa, the volume ratio of hydrogen oil is 1000:1, and during liquid, volume space velocity is 1.0h
-1; Hydrocracking reaction afterproduct enters fractionating column again and cuts diesel oil distillate after high-low pressure separator is separated.The diesel oil distillate prepared by the present embodiment detects, and the character of diesel oil distillate is as shown in table 1.
Comparative example 1
The cut being less than 360 DEG C is cut by after coal tar Atmospheric vacuum pre-distillation; Described cut is carried out hydro-upgrading reaction in the first reactor, the catalyst for hydro-upgrading that catalyst used adopts embodiment 3 to prepare, reaction temperature is 360 DEG C, and reaction pressure is 15.0MPa, and the volume ratio of hydrogen oil is 900:1, and during liquid, volume space velocity is 1.0h
-1; Hydro-upgrading reaction afterproduct enters fractionating column again and cuts diesel oil distillate after high-low pressure separator is separated.The diesel oil distillate prepared by the present embodiment detects, and the character of diesel oil distillate is as shown in table 1.
Comparative example 2
The cut being less than 360 DEG C is cut by after coal tar Atmospheric vacuum pre-distillation; Described cut is directly entered in the second reactor and carry out hydro-upgrading reaction (without the first reactor), the hydrocracking catalyst that catalyst used adopts embodiment 3 to prepare, reaction temperature is 390 DEG C, pressure is 17.0MPa, the volume ratio of hydrogen oil is 1000:1, and during liquid, volume space velocity is 1.0h
-1; Hydrocracking reaction afterproduct enters fractionating column again and cuts diesel oil distillate after high-low pressure separator is separated.The diesel oil distillate prepared by the present embodiment detects, and the character of diesel oil distillate is as shown in table 1.
The performance data table of diesel oil distillate prepared by table 1 embodiment 4 ~ 6 and comparative example 1 ~ 2
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (4)
1. coal tar hydrogenating produces a process for diesel oil distillate, comprises the following steps:
The cut of less than 360 DEG C will be cut after coal tar air-distillation;
The cut of less than 360 DEG C is carried out hydro-upgrading reaction and hydrocracking reaction successively;
The catalyst of described hydro-upgrading reaction comprises: the molybdenum oxide of 2wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus; The temperature of described hydro-upgrading reaction is 350 DEG C ~ 380 DEG C, and pressure is 10.0MPa ~ 16.0MPa, and hydrogen to oil volume ratio is (800 ~ 1000): 1, and air speed is 0.8h
-1~ 1.0h
-1;
The catalyst of described hydrocracking reaction comprises: the tungsten oxide of 3wt% ~ 9wt%, the cobalt oxide of 2wt% ~ 6wt%, the nickel oxide of 2wt% ~ 9wt%, the activated alumina of surplus; The temperature of described hydrocracking reaction is 350 DEG C ~ 400 DEG C, and pressure is 15.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is (900 ~ 1100): 1, and air speed is 1.0h
-1~ 1.2h
-1;
Product after hydrocracking is carried out fractionation again after high-low pressure separation, obtain diesel oil distillate.
2. process according to claim 1, is characterized in that, the specific area of the catalyst of described hydro-upgrading reaction is 180m
2/ g ~ 250m
2/ g, pore volume is 0.5ml/g ~ 0.8ml/g.
3. process according to claim 1, is characterized in that, the specific area of the catalyst of described hydrocracking reaction is 180m
2/ g ~ 250m
2/ g, pore volume is 0.6ml/g ~ 0.8ml/g.
4. process according to claim 1, is characterized in that, described in the catalyst of described hydro-upgrading reaction, the granularity of activated alumina is 40nm ~ 50nm; The granularity of activated alumina described in the catalyst of described hydrocracking reaction is 40nm ~ 50nm.
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