CN103301872B - A kind of unsulfided catalyst and preparation method thereof and application - Google Patents
A kind of unsulfided catalyst and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of unsulfided catalyst and preparation method thereof.Described catalyst is made up of modified Y molecular sieve, nickel oxide and little porous aluminum oxide; The mass ratio of described modified Y molecular sieve, described nickel oxide and described little porous aluminum oxide is 10.0 ~ 35.0:3.0 ~ 30.0:35.0 ~ 87.0.After described method comprises the steps: the aqueous solution of described modified Y molecular sieve and nickeliferous soluble-salt to pull an oar with described little porous aluminum oxide successively through modulating, kneading and roll agglomerating; Then carry out extruded, more namely drying and roasting obtain described unsulfided catalyst successively.Unvulcanised state hydrocracking catalyst provided by the invention, environmental protection, preparation technology and raw material are simple, cost is low, and are suitable for preparing high metals content catalysts.
Description
Technical field
The present invention relates to a kind of unsulfided catalyst and preparation method thereof and application.
Background technology
Along with the change of oil product consumption structure, the intermediate oils such as diesel oil day by day come into one's own in oil product consumption, and environmental requirement also increasingly stringent, the production of clean engine fuel is made also to become more and more important, the engine fuel that catalytic cracking obtains generally is difficult to the requirement that touches the mark, and quality is better, the straight run that can be used as blend component is also more and more unable to make ends meet, thus can the production high-quality middle oil type hydrocracking process that cleans engine fuel more and more be paid attention to.
The ratio of low temperature F-T sintetics not only straight-chain hydrocarbons is higher, and heavy hydrocarbon (>370 DEG C) is selective higher, generally selective about 50%.The feature of F-T sintetics determines intermediate oil and by-product high-quality lube base oil, the naphtha of the cleaning of low temperature F-T synthesis technique (LHFT) the most applicable large-scale production high-quality, and 160 ~ 260 ° of C fraction section that fractionation obtains can be used as high-quality aviation kerosine blend component.
CN1382772A discloses a kind of method of DCL/Direct coal liquefaction greatly preparing hihg-quality diesel oil and jet fuel, but the Cetane number of product diesel oil only can reach about 45, can not meet Europe II diesel oil standard; CN1594509A etc. the heavy hydrocarbon of F-T artificial oil and/or kettle bottom wax are adopted Fe catalyst based in suspension bed hydro-conversion produce naphtha and diesel oil, because suspension bed technique Hydrogenation is more weak, severe reaction conditions, product property needs to improve further.The method that it is diesel oil that USP5689031 introduces the production of F-T artificial oil, this patent proposes to retain a small amount of oxygenatedchemicals in F-T oil, improves the greasy property of combined diesel oil, but operates comparatively complicated.USP5378348 proposes a kind of method of mainly being produced by F-T artificial oil as jet fuel, and in patent weak point flow process, lock out operation is more, and long flow path, energy consumption is large.Therefore F-T synthesis heavy distillate and/or wax are obtained high-quality diesel oil and the high-quality such as naphtha, jet fuel industrial chemicals is one of important technical links through hydrocracking, develop the most applicable catalyst the most key.
The hydrocracking catalyst major part that commercial plant uses at present is the catalyst containing zeolite, and the zeolite component adopted mainly y-type zeolite.Raw material y-type zeolite, after modification, is used in middle oil type hydrocracking catalyst, has reasonable activity and middle distillates oil selectivity.US6174430 and US5366615 describes respectively and adopts a kind of Nobel metal hydrogen cracking catalyst containing USY molecular sieve to produce naphtha and jet fuel, and because the USY molecular sieve acidity used is high, therefore middle distillates oil selectivity is poor.US5190903 discloses the low acidity Y zeolite being generally used for middle oil type hydrocracking catalyst, and object is the middle distillates oil selectivity improving catalyst, and its feature is to employ a kind of NH
3-TPD acidity is preferably less than 1.5mmol/g low acidity Y zeolite, and conversion rate control is when 85wt%, and reaction temperature is up to 405 ° of C-425 ° of C, and middle distillates oil selectivity only has 55 ~ 63%, and catalyst middle distillates oil selectivity improves not obvious.Although for many years improve catalyst activity, selective on have larger progress, comparatively ten-strike is achieved from improvement acidity of catalyst component aspect, have numerous catalyst to drop into commercial Application, but the improvement performance of acidic components and the coupling of regulating catalyst acid function-metal function are still the direction of research further further.
In addition, in existing oil hydrogenation catalyst cracking process, mostly adopt immersion-type hydrocracking catalyst, then this immersion-type hydrocracking catalyst is obtained through heat resolve by component impregnated activated on carrier, but the tenor of Kaolinite Preparation of Catalyst is very restricted.Before this catalyst is used for oil hydrocracked, treated, also need to carry out presulfurization process, active component uses with the form of sulfide, and this is necessary step in existing oil hydrocracking.But the process of carrying out presulfurization before catalyst uses will inevitably to environment and destruction.Especially for the hydrocracking without sulphur Fischer-Tropsch synthesis of heavy hydrocarbon, research and development one does not need to carry out presulfurization, simple and the catalyst that tenor load capacity is controlled of preparation technology, reduce for environment pollution and cost-saving etc. all there is important theory significance and industrial application value.
Summary of the invention
The object of this invention is to provide a kind of unsulfided catalyst and preparation method thereof and application, method technique of the present invention is simple, tenor in the catalyst obtained is unrestricted, and there is good environment protecting, and obtain the fuel oil of high-quality, ultra-clean in the hydrocracking of F-T heavy hydrocarbon.
A kind of unsulfided catalyst provided by the present invention, is made up of modified Y molecular sieve, nickel oxide and little porous aluminum oxide;
The mass ratio of described modified Y molecular sieve, described nickel oxide and described little porous aluminum oxide is 10.0 ~ 35.0:3.0 ~ 30.0:35.0 ~ 87.0.
In above-mentioned unsulfided catalyst, described modified Y molecular sieve has following physicochemical property:
SiO
2/ Al
2o
3mol ratio can be 20 ~ 200, specifically can be 80 ~ 186,80,98,121,153 or 186; Specific surface can be 700 ~ 950m
2/ g, specifically can be 750.89 ~ 906.7m
2/ g, 750.89m
2/ g, 872.3m
2/ g, 880.5m
2/ g, 897.2m
2/ g or 906.7m
2/ g; Infrared acidity can be 0.05 ~ 0.7mmol/g, specifically can be 0.19 ~ 0.65mmol/g, 0.19mmol/g, 0.38mmol/g, 0.43mmol/g, 0.57mmol/g or 0.65mmol/g; Na
2mass percentage≤0.1% of O, as 0.08%, 0.05%, 0.02%, 0.01% or 0.1%; Pore volume can be 0.35 ~ 0.65mL/g, specifically can be 0.38mL/g, 0.40mL/g, 0.50mL/g, 0.57mL/g or 0.60mL/g; Cell parameter can be 24.25 ~ 24.45 dusts, degree of crystallinity >95%, specifically can be 98.2%, 98.9%, 99.3% or 107.5%.
In above-mentioned unsulfided catalyst, described little porous aluminum oxide has following physicochemical property: pore volume can be 0.2 ~ 0.75ml/g, specifically can be 0.3 ~ 0.55ml/g, 0.49ml/g, 0.51ml/g, 0.52ml/g or 0.53ml/g, specific area can be 150 ~ 400m
2/ g, specifically can be 230 ~ 350m
2/ g, 258.2m
2/ g, 258.7m
2/ g, 272.3m
2/ g, 320.6m
2/ g or 341.7m
2/ g.
The present invention still further provides the preparation method of above-mentioned unsulfided catalyst, comprises the steps:
After the aqueous solution of described modified Y molecular sieve and nickeliferous soluble-salt is pulled an oar with described little porous aluminum oxide successively through modulating, kneading and roll agglomerating; Then carry out extruded, more namely drying and roasting obtain described unsulfided catalyst successively.
In above-mentioned preparation method, described modified Y molecular sieve crosses 200 mesh sieves.
In above-mentioned preparation method, described nickeliferous soluble-salt can be nickelous carbonate, nickel nitrate or nickel acetate.
In above-mentioned preparation method, the temperature of described drying can be 100 ~ 150 ° of C, and specifically can be 100 ° of C, 110 ° of C, 120 ° of C, 130 ° of C or 150 ° C, the time can be 2 ~ 6h, specifically can be 4h, 5h or 6h; The temperature of described roasting can be 400 ~ 550 ° of C, and specifically can be 420 ° of C, 450 ° of C, 480 ° of C, 500 ° of C or 550 ° C, the time can be 2 ~ 6h, specifically can be 2h, 3h or 4h.
Unsulfided catalyst provided by the invention can be used for hydrocracking process, be specially adapted to the process that intermediate oil is prepared in Tscher-Topsch synthesis of heavy wax hydrocracking, its reaction condition can be: reaction pressure can be 3.0 ~ 15.0Mpa, hydrogen to oil volume ratio (hydrogen namely passed into and the volume ratio of feedstock oil) can be 400 ~ 1500, and volume space velocity can be 5 ~ 10.0h
-1, reaction temperature can be 320 ~ 400 ° of C.
The present invention compared with prior art, has the following advantages:
(1) catalyst provided by the invention has well selective to intermediate oil, and be conducive to the effective conversion of Tscher-Topsch synthesis of heavy wax to intermediate oil, by-product naphtha, lube base oil are high-quality industrial chemicals.
(2) catalyst provided by the invention is when hydrocracking, and 160 ~ 260 DEG C of fraction section product selectivity are high, condensation point <-51 ° of C, is the boat coal blend component of high-quality.
(3) unvulcanised state hydrocracking catalyst provided by the invention, environmental protection, preparation technology and raw material are simple, cost is low, and are suitable for preparing high metals content catalysts.
(4) when the large air speed of catalyst provided by the invention operates, good catalyst activity, good stability.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, hydrocracking catalyst HC-1
Take porphyrize to sieve 200 object Modified Zeolite Y (SiO
2/ Al
2o
3mol ratio is 80, Na
2o content is 0.02w%, cell parameter 24.33 dust, and specific surface is 750.89m
2/ g, infrared acidity is 0.65mmol/g, pore volume is 0.38mL/g, degree of crystallinity is 98.2%) 15g(butt), 33.32g nickel acetate to be dissolved in a certain amount of water and standard configuration solution to 70mL, the aqueous solution of nickel acetate is added making beating in Modified Zeolite Y even, with binding agent little porous aluminum oxide 75g(butt) (specific area 258.7m
2/ g, pore volume 0.49ml/g) modulation, kneading roll agglomerating after, extrusion becomes column type, catalyst diameter 1.4mm.By dry 4h under it in an oven 120 ° of C, be cooled to room temperature after 420 ° of C roasting 4h, just can obtain catalyst HC-1.
Wherein the mass percent of each component consists of: Modified Zeolite Y: aluminium oxide: nickel oxide=15.0:75.0:10.0.
Catalyst HC-1 prepared by use the present embodiment is for heavy wax hydrocracking reaction, and reaction condition is: reaction pressure is 10.0Mpa, and hydrogen to oil volume ratio is 500, and air speed is 10.0h
-1, reaction temperature is 365 ° of C.
Feedstock oil character is as shown in table 1, and the evaluation result of catalyst HC-1 is as shown in table 2.
The preparation of embodiment 2, hydrocracking catalyst HC-2
Take porphyrize to sieve 200 object modified Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 98, Na
2o content is 0.01w%, cell parameter 24.32 dust, and specific surface is 880.5m
2/ g, infrared acidity is 0.57mmol/g, pore volume is 0.46mL/g, degree of crystallinity is 107.5%) 20g(butt), 49.97g nickel acetate to be dissolved in a certain amount of water and standard configuration solution to 70mL, the aqueous solution of nickel acetate is added making beating in Modified Zeolite Y even, with binding agent little porous aluminum oxide 65g(butt) (specific area 320.6m
2/ g, pore volume 0.52ml/g) modulation, kneading to paste, extrusion becomes trifolium-shaped, catalyst diameter 1.7mm.By dry 5h under it in an oven 100 ° of C, be cooled to room temperature after 450 ° of C roasting 4h, just can obtain catalyst HC-2.
Wherein the mass percent of each component consists of: Modified Zeolite Y: aluminium oxide: nickel oxide=20.0:65.0:15.0.
Catalyst HC-2 prepared by use the present embodiment is for heavy wax hydrocracking reaction, and reaction condition is: reaction pressure is 8.0Mpa, and hydrogen to oil volume ratio is 600, and air speed is 8.0h
-1, reaction temperature is 362 ° of C.
Feedstock oil character is as shown in table 1, and the evaluation result of catalyst HC-2 is as shown in table 2.
The preparation of embodiment 3, hydrocracking catalyst HC-3
Take porphyrize to sieve 200 object modified Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 121, Na
2o content is 0.05w%, cell parameter 24.37 dust, and specific surface is 872.3m
2/ g, infrared acidity is 0.43mmol/g, pore volume is 0.50mL/g, degree of crystallinity is 98.9%) 25g(butt), 66.63g nickel acetate to be dissolved in a certain amount of water and standard configuration solution to 70mL, the aqueous solution of nickel acetate is added making beating in Modified Zeolite Y even, with binding agent little porous aluminum oxide 55g(butt) (specific area 272.3m
2/ g, pore volume 0.51ml/g) modulation, kneading rolls agglomerating, and extrusion becomes butterfly-type, catalyst diameter 1.8mm.By dry 6h under it in an oven 110 ° of C, be cooled to room temperature after 480 ° of C roasting 3h, just can obtain catalyst HC-3.
Wherein the mass percent of each component consists of: Modified Zeolite Y: aluminium oxide: nickel oxide=25.0:55.0:20.0.
Catalyst HC-3 prepared by use the present embodiment is for heavy wax hydrocracking reaction, and reaction condition is: reaction pressure is 4.0Mpa, and hydrogen to oil volume ratio is 1000, and air speed is 6.0h
-1, reaction temperature is 363 ° of C.
Feedstock oil character is as shown in table 1, and the evaluation result of catalyst HC-3 is as shown in table 2.
The preparation of embodiment 4, hydrocracking catalyst HC-4
Take porphyrize to sieve 200 object modified Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 153, Na
2o content is 0.10w%, cell parameter 24.30 dust, and specific surface is 897.2m
2/ g, infrared acidity is 0.38mmol/g, pore volume is 0.57mL/g, degree of crystallinity is 99.3%) 30g(butt), 83.29g nickel acetate to be dissolved in a certain amount of water and standard configuration solution to 70mL, the aqueous solution of nickel acetate is added making beating in Modified Zeolite Y even, with binding agent little porous aluminum oxide 45g(butt) (specific area 258.2m
2/ g, pore volume 0.49ml/g) modulation, kneading rolls agglomerating, extrusion spheroiding, catalyst diameter 2.0mm.By dry 5h under it in an oven 130 ° of C, be cooled to room temperature after 500 ° of C roasting 3h, just can obtain catalyst HC-4.
Wherein the mass percent of each component consists of: Modified Zeolite Y: aluminium oxide: nickel oxide=30.0:45.0:25.0.
Catalyst HC-4 prepared by use the present embodiment is in heavy wax hydrocracking reaction, and reaction condition is: reaction pressure is 12.0Mpa, and hydrogen to oil volume ratio is 1200, and air speed is 7.0h
-1, reaction temperature is 366 ° of C.
Feedstock oil character is as shown in table 1, and catalyst HC-4 evaluation result is as shown in table 2.
The preparation of embodiment 5, hydrocracking catalyst HC-5
Take porphyrize to sieve 200 object Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 186, Na
2o content 0.08w%, cell parameter 24.28 dust, specific surface is 906.7m
2/ g, infrared acidity is 0.19mmol/g, pore volume is 0.65mL/g, degree of crystallinity is 98.9%) 35g(butt), 99.95g nickel acetate to be dissolved in a certain amount of water and standard configuration solution to 70mL, the aqueous solution of nickel acetate is added making beating in Y zeolite even, with binding agent little porous aluminum oxide 35g(butt) (specific area 341.7m
2/ g, pore volume 0.53ml/g) modulation, kneading rolls agglomerating, and extrusion becomes trifolium-shaped, catalyst diameter 2.0mm.By dry 4h under it in an oven 150 ° of C, be cooled to room temperature after 550 ° of C roasting 2h, just can obtain catalyst HC-5.
Wherein the mass percent of each component consists of: Modified Zeolite Y: aluminium oxide: nickel oxide=35.0:35.0:30.0.
Use catalyst HC-5 heavy wax hydrocracking reaction prepared by the present embodiment, reaction condition is: reaction pressure is 15.0Mpa, and hydrogen to oil volume ratio is 1500, and air speed is 5.0h
-1, reaction temperature is 358 ° of C.
Feedstock oil character is as shown in table 1, and catalyst HC-5 valency result is as shown in table 2.
Data as can be seen from table 2, when the catalyst conversion per pass adopting the present invention to prepare is 50%, intermediate oil yield is high, and 160 ~ 260 ° of C fraction section that cracked product fractionation obtains, selective height, condensation point is low, be high-quality clean boat coal blend component, so unvulcanised state hydrocracking catalyst provided by the invention, environmental protection, preparation technology is simple, cost is low, when the large air speed of catalyst operates, good catalyst activity.
Table 1 feedstock oil character
Table 2 experimental result
Below describe embodiment of the present invention in detail, a lot of improvement can be done for a person skilled in the art obviously and change and do not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (6)
1. the preparation method of unsulfided catalyst, comprises the steps:
After the aqueous solution of modified Y molecular sieve and nickeliferous soluble-salt is pulled an oar with little porous aluminum oxide successively through modulating, kneading and roll agglomerating; Then carry out extruded, more namely drying and roasting obtain unsulfided catalyst successively;
Described unsulfided catalyst is made up of modified Y molecular sieve, nickel oxide and little porous aluminum oxide; The mass ratio of described modified Y molecular sieve, described nickel oxide and described little porous aluminum oxide is arbitrary described mass ratio in following (1)-(4):
(1)20.0：15.0：65.0；
(2)25.0：20.0：55.0；
(3)30.0：25.0：45.0；
(4)35.0：30.0：35.0。
2. preparation method according to claim 1, is characterized in that: described modified Y molecular sieve crosses 200 mesh sieves.
3. preparation method according to claim 1 and 2, is characterized in that: described nickeliferous soluble-salt is nickelous carbonate, nickel nitrate or nickel acetate.
4. preparation method according to claim 1 and 2, is characterized in that: the temperature of described drying is 100 ~ 150 DEG C, and the time is 2 ~ 6h;
The temperature of described roasting is 400 ~ 550 DEG C, and the time is 2 ~ 6h.
5. preparation method according to claim 1 and 2, is characterized in that: described modified Y molecular sieve has following physicochemical property:
SiO
2/ Al
2o
3mol ratio be 20 ~ 200; Specific surface is 700 ~ 950m
2/ g; Infrared acidity is 0.05 ~ 0.7mmol/g; Na
2mass percentage≤0.1% of O, pore volume is 0.35 ~ 0.65mL/g, and cell parameter is 24.25-24.45 dust, degree of crystallinity >95%.
6. preparation method according to claim 1 and 2, is characterized in that: described little porous aluminum oxide has following physicochemical property:
Pore volume is 0.2 ~ 0.75ml/g, and specific area is 150 ~ 400m
2/ g.
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| CN1064862C (en) * | 1994-11-09 | 2001-04-25 | 中国石油化工总公司 | Hydrogen cracking catalyst |
| US6093672A (en) * | 1997-03-20 | 2000-07-25 | Shell Oil Company | Noble metal hydrocracking catalysts |
| CN1136298C (en) * | 2001-03-09 | 2004-01-28 | 中国科学院山西煤炭化学研究所 | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use |
| CN100417713C (en) * | 2006-05-23 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Hydrocracking catalyst for Tscher-Topsch synthesis of heavy wax, its preparation method and application thereof |
| CN101380589B (en) * | 2007-09-04 | 2011-07-20 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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