CN102553638A - Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst - Google Patents
Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst Download PDFInfo
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Abstract
The invention relates to a double-microporous-mesoporous composite molecular sieve hydrocracking catalyst, which is composed of a Y-Beta/MCM-41 double-microporous-mesoporous composite molecular sieve, amorphous silicon aluminum, macroporous alumina, a bonder, an extrusion assistant agent, VIB family metal oxide, VIII family metal oxide and VA family element oxide. The catalyst is characterized by utilizing the Y-Beta/MCM-41 double-micropore-mesoporous compositie molecular sieve which combines the advantages of Y and Beta microporous molecular sieves and a MCM-41 mesoporous molecular sieve to serve as a main acid component, the composite molecular sieve adopts cetyl trimethyl ammonium bromide and alkylphenol ethoxylate mixed solution to serve as a template, leads in Y and Beta double-microporous phases which are pretreated and silicon sources and/or aluminum sources which synthetize a MCM-41 mesoporous phase, and the catalyst is obtained through hydrothermal crystallization treatment. The double-microporous-mesoporous composite molecular sieve hydrocracking catalyst has high catalysis activation and can produce high-quality products including naphtha, diesel, tail oil and the like.
Description
Technical field
The present invention relates to a kind of pair of microporous-mesoporous composite molecular sieve hydrocracking catalyst.
Background technology
The main feature of hydrocracking technology is that adaptability to raw material is strong, products scheme flexibly, high, the good product quality of purpose product selectivity and added value be high, but multiple high-quality oil product of Direct Production (for example gasoline, diesel oil, lube base wet goods) and high-quality industrial chemicals (for example heavy naphtha, hydrocracking tail oil etc.).Therefore; Along with crude quality year by year variation and market to the sustainable growth of high-quality oil product and high-quality chemical industry raw materials requirement amount and the appearance in succession of new environmental regulation; The importance of hydrocracking technology becomes increasingly conspicuous; Use also increasingly extensively, become and rationally utilized limited petroleum resources, produce cleaning oil product and the optimum oil Refining Technologies of high-quality industrial chemicals to greatest extent.
Hydrocracking catalyst is a kind of bifunctional catalyst with hydrogenating function and cracking function, generally adopts base metal to load on the acid carrier material and processes.Carrier material is generally amorphous aluminum silicide and/or micro porous molecular sieve, and the hydrocracking catalyst major part of using at present on the commercial plant all contains micro porous molecular sieve, and the molecular sieve that uses mainly is modification Y type and Beta type micro porous molecular sieve.Because the micro porous molecular sieve aperture is less; The molecule that diameter is bigger in the reaction raw materials is difficult to be diffused into molecular sieve pore passage inside; And the rapid diffusion that less pore passage structure also influences reaction afterproduct molecule overflows, thereby causes secondary cracking, reduces liquid product yield.The aperture addresses this problem appearing as of 2nm～50nm mesopore molecular sieve new approaches is provided.But because the mesopore molecular sieve hole wall is amorphous, it is acid and hydrothermal stability is far short of what is expected than micro porous molecular sieve, this big limitations its as the application of catalysis material in petroleum chemical industry.Therefore the researcher hopes to combine micropore, mesoporous two kinds of molecular sieves advantage separately, synthesizing new microporous-mesoporous composite molecular sieve material.Microporous-mesoporous composite molecular sieve has micropore and mesoporous dual model pore structure, in conjunction with the advantages such as highly acid and high hydrothermal stability of duct advantage and poromerics of mesoporous material, can make two kinds of materials synergies and has complementary advantages.This type of composite molecular screen material is applied to hydrocracking catalyst, will improve the catalytic performance of catalyst greatly.
US5,536,687 have introduced the hydrocracking catalyst of a kind of Y of containing and Beta molecular sieve, used Y molecular sieve (like LZ-10, silica alumina ratio 4.5～5.2) cell parameter of this catalyst less than
Used Beta molecular sieve silica alumina ratio 20～30, the gross weight of Y and Beta accounts for 8%～20% of catalyst weight, the ratio of the two preferably 1: 1, this agent reactivity is lower slightly, at air speed 1.0h
-1The time, reaction temperature is generally more than 392 ℃.
US5,350,501 have introduced a kind of hydrocracking catalyst that contains Y molecular sieve and Beta molecular sieve, and it consists of Y molecular sieve content 20%～40%, and the ratio of Beta and Y is 1: 2～2: 1, MoO
3Content 8～30%, NiO content 3～10%, all the other are aluminium oxide, when being used to produce intermediate oil, Y content 1%～15%, Beta content 1%～15%, the Beta molecular sieve that here uses is Hydrogen, and is acid strong, so middle distillates oil selectivity is lower.And this agent operating condition is harsh, needs at NH
3Concentration is less than carrying out under the 200ppm atmosphere.
It is the hydrocracking catalyst of carrier that CN1488726A has introduced a kind of composite molecular screen with amorphous aluminum silicide, Y and SAPO-11, adopts the coprecipitation preparation.This agent catalytic activity is lower, and initial reaction temperature is 404 ℃～406 ℃.
Summary of the invention
The objective of the invention is to develop a kind of two microporous-mesoporous composite molecular sieves and non-noble metal hydrocracking catalyst of load of containing, be used to handle heavy hydrocarbon chargings such as VGO, CGO.
Hydrocracking catalyst of the present invention is a carrier with two microporous-mesoporous composite molecular sieves, amorphous aluminum silicide and macroporous aluminium oxide, is the hydrogenation activity component with VI B family's metal and VIII family metal, adds V A family's element and extrusion aid simultaneously.By catalyst carrier weight 100%, two microporous-mesoporous composite molecular sieves are 5～30%, and amorphous aluminum silicide is 20～60%, and macroporous aluminium oxide is 5～30%, and binding agent is 10～25%, and extrusion aid is 2～5%.By catalyst weight 100%, VI B family metal oxide is 10～30%, and the VIII family metal oxide is 5～10%, and V A family element oxide is 0.1～10%.
Of the present invention pair of microporous-mesoporous composite molecular sieve is the Y-Beta/MCM-41 composite molecular screen, and wherein the mass ratio of Y and Beta is 1: 2～5: 1, and the relative mass content of micropore phase is 20～70%.
The specific area 600m of of the present invention pair of microporous-mesoporous composite molecular sieve
2/ g～950m
2/ g, pore volume 0.5ml/g～0.8ml/g, meleic acid amount 0.05mmol/g～0.5mmol/g.
Of the present invention pair of microporous-mesoporous composite molecular sieve preparation process is following:
With Y and Beta molecular sieve and deionized water mixing stirring; Join then in the mixed solution of softex kw and APES and go, after stirring, drip silicon source and aluminium source solution; The pH value of adjustment system is 8～12; After the system of treating is stable material is transferred in the crystallizing kettle 80 ℃～120 ℃, crystallization 24h～72h, suction filtration, oven dry, roasting obtain the two microporous-mesoporous composite molecular sieves of Hydrogen Y-Beta/MCM-41 again after the ammonium exchange.
Among the preparation method of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 of the present invention, the SiO of Y molecular sieve
2/ Al
2O
3Mol ratio is 4～20, and specific area is 500m
2/ g～800m
2/ g, pore volume are 0.4ml/g～0.7ml/g; The SiO of above-mentioned Beta molecular sieve
2/ Al
2O
3Mol ratio is 20～50, and specific area is 400m
2/ g～700m
2/ g, pore volume are 0.35ml/g～0.5ml/g.
Among the preparation method of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 of the present invention, proportioning raw materials in molar ratio, CTAB/SiO
2Be 0.10～0.25, CTAB/OP-10 is 5～7, SiO
2/ H
2O is 58～78, Si/Al>=25; Press mass ratio (Y+Beta)/SiO
2Be 0.26～0.80, Y and Beta molecular sieve consumption can carry out the adjusting of arbitrary proportion.
Among the preparation method of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 of the present invention, the silicon source is the mixture of any in sodium metasilicate, industrial-grade sodium silicate or the Ludox or two kinds; The aluminium source is the mixture of any in aluminium chloride, aluminum sulfate or the aluminum nitrate or two kinds.
The mass percent of silica is 20～60% in the amorphous aluminum silicide of the present invention, is preferably 30～40%; Specific area is 250m
2/ g～550m
2/ g is preferably 300m
2/ g～450m
2/ g; Pore volume is 0.5ml/g～1.2ml/g, is preferably 0.8ml/g～1.0ml/g.
Macroporous aluminium oxide of the present invention, specific area are 250m
2/ g～550m
2/ g is preferably 350m
2/ g; Pore volume is 0.8ml/g～1.2ml/g, is preferably 0.9ml/g～1.0ml/g.
Binding agent of the present invention is mixed and made into by little porous aluminum oxide and acid solution, and the mol ratio of the hydrogen ion in the acid, water and little porous aluminum oxide is 0.3: 5: 1.Aperture aluminium oxide specific area is 100m
2/ g～400m
2/ g is preferably 150m
2/ g～350m
2/ g; Pore volume 0.25ml/g～0.6ml/g is preferably 0.3ml/g～0.5ml/g; The used acid of acid solution comprises one or more in hydrochloric acid, sulfuric acid, phosphoric acid, the nitric acid.
Extrusion aid of the present invention is the sesbania powder.
VI B of the present invention family metallic element is W and/or Mo, and VIII family metallic element is Ni and/or Co.
V A of the present invention family element is P, and it can be by phosphoric acid, P
2O
5, mode such as phosphate introduces.
The moulding of hydrocracking catalyst of the present invention and metal mode of loading mainly are to adopt after the extrusion method of impregnating metal again; Dipping method can be incipient impregnation or supersaturation dipping; Can adopt co-impregnation or step impregnation method; Dipping method is not construed as limiting the invention, and concrete preparation method is following:
Two microporous-mesoporous composite molecular sieves, amorphous aluminum silicide, macroporous aluminium oxide, adhesive and the extrusion aid that (1) will the present invention relates to mix; Extruded moulding; Support shapes is generally cylindrical after the extrusion; Also can process special-shaped bars such as clover or bunge bedstraw herb shape, with above-mentioned carrier behind 80 ℃～150 ℃ dry 2h～4h, 400 ℃～600 ℃ roasting 4h～8h.
(2) salt and the V A family element of getting VI B family's metallic element and VIII metallic element are prepared maceration extract, with the carrier strip that the maceration extract of gained floods (1) gained, dip time 1h～4h.
(3) behind 80 ℃～150 ℃ dry 2h～4h of carrier strip that the dipping of (2) gained is good, 400 ℃～600 ℃ roasting 4h～8h obtain the finished product hydrocracking catalyst.
Catalyst of the present invention is used for hydrocracking process; Be fit to normal pressure wax oil, decompressed wax oil, wax tailings, depitching wet goods heavier feeds; The material boiling range is 300 ℃～550 ℃, in the raw material＞350 ℃ of cut percents by volume are best ≮ and 60%, nitrogen content 500 μ g/g～2000 μ g/g.
Catalyst of the present invention generally adopts the hydrocracking process flow process of one-stage serial, and wherein, the hydrogenation prerefining is used for removing the most of the nitrogen and the saturated polycyclic aromatic hydrocarbon of feedstock oil.
Catalyst of the present invention need carry out presulfurization and handle before handling heavier feeds, and process conditions are 300 ℃～450 ℃ of reaction temperatures, hydrogen partial pressure 8Mpa～20MPa, and hydrogen to oil volume ratio is 500: 1～2000: 1, volume space velocity 0.5h during liquid
-1～3.0h
-1
Catalyst of the present invention is applicable to hydrocracking fecund intermediate oil, is that catalyst has greater activity under 60%～75% the condition at＞350 ℃ of distillate conversion per pass of control, have simultaneously the heavy naphtha virtue dive high, advantage such as tail oil BMCI value is low.
The specific embodiment
Embodiment 1
Synthesizing of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41
With 3.1g Y (SiO
2/ Al
2O
3Mol ratio is 5.32) and 6.2g Beta (SiO
2/ Al
2O
3Mol ratio is about 30) molecular sieve and 400ml deionized water join in the 200ml mixed solution that is dissolved with 16g CTAB and 5g OP-10 after mixing, in stirring at room 30min, in mixed liquor, slowly drip then and be dissolved with 35.7g Na
2SiO
350ml solution, the back that stirs slowly adds and is dissolved with 7.8gAl
2(SO
4)
318H
2The 20ml solution of O, feed molar proportioning are 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.004Al
2O
3: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.53.The back adjustment system pH that stirs is 10.5; Continue to stir behind the 1.0h mixed liquor is packed in the 1L crystallization still of being with liner, in 110 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting; Product of roasting is exchanged 3.0h with 1: 300 ratio at the ammonium nitrate solution intermediate ion of 0.05mol/L; Suction filtration, oven dry, roasting promptly get Y and Beta ratio be 1: 2, micropore mutually relative amount be 53wt%, the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41, this sample called after A.The specific area of this sample is 867m
2/ g, pore volume are 0.81ml/g, and average pore size is 3.7nm.
Embodiment 2
Synthesizing of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41
With 2.35g Y (SiO
2/ Al
2O
3Mol ratio is 5.32) and 2.35g Beta (SiO
2/ Al
2O
3Mol ratio is about 30) molecular sieve and 200ml deionized water join in the 100ml mixed solution that is dissolved with 8g CTAB and 2.5g OP-10 after mixing, in stirring at room 30min, in mixed liquor, slowly drip then and be dissolved with 35.4g Na
2SiO
350ml solution, the back that stirs slowly adds and is dissolved with 3.9g Al
2(SO
4)
318H
2The 20ml solution of O, feed molar proportioning are 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.004Al
2O
3: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.27.The back adjustment system pH that stirs is 10.5; Continue to stir behind the 1.0h mixed liquor is packed in the 1L crystallization still of being with liner, in 110 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting; Product of roasting is exchanged 3.0h with 1: 300 ratio at the ammonium nitrate solution intermediate ion of 0.05mol/L; Suction filtration, oven dry, roasting promptly get Y and Beta ratio be 1: 1, micropore mutually relative amount be 27wt%, the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41, this sample called after B.The specific area of this sample is 751m
2/ g, pore volume are 0.89ml/g, and average pore size is 4.6nm.
Embodiment 3
Synthesizing of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41
With 6.2g Y (SiO
2/ Al
2O
3Mol ratio is 5.32) and 3.1g Beta (SiO
2/ Al
2O
3Mol ratio is about 30) join in the 200ml mixed solution that is dissolved with 16g CTAB and 5g OP-10 after molecular sieve and the 400ml deionized water mixing preliminary treatment, in stirring at room 30min, in mixed liquor, slowly drip then and be dissolved with 35.7g Na
2SiO
350ml solution, the back that stirs slowly adds and is dissolved with 7.8gAl
2(SO
4)
318H
2The 20ml solution of O, feed molar proportioning are 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.004Al
2O
3: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.53.Back adjustment system pH 10.5 stirs; Continue to stir behind the 1.0h mixed liquor is packed in the 1L crystallization still of being with liner, in 110 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting; Product of roasting is exchanged 3.0h with 1: 300 ratio at the ammonium nitrate solution intermediate ion of 0.05mol/L; Suction filtration, oven dry, roasting promptly get Y and Beta ratio be 2: 1, micropore mutually relative amount be 53wt%, the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41, this sample called after C.The specific area of this sample is 816m
2/ g, pore volume are 0.76ml/g, and average pore size is 3.6nm.
Embodiment 4
Synthesizing of the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41
With 3.8g Y (SiO
2/ Al
2O
3Mol ratio is 5.32) and 0.95g Beta (SiO
2/ Al
2O
3Mol ratio is about 30) join in the 200ml mixed solution that is dissolved with 8g CTAB and 2.5gOP-10 after molecular sieve and the 400ml mixing preliminary treatment, in stirring at room 30min, in mixed liquor, slowly drip then and be dissolved with 35.4g Na
2SiO
350ml solution, the back that stirs slowly adds and is dissolved with 3.9gAl
2(SO
4)
318H
2The 20ml solution of O, feed molar proportioning are 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.004Al
2O
3: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.27.Back adjustment system pH 10.5 stirs; Continue to stir behind the 1.0h mixed liquor is packed in the 1L crystallization still of being with liner, in 110 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting; Product of roasting is exchanged 3.0h with 1: 300 ratio at the ammonium nitrate solution intermediate ion of 0.05mol/L; Suction filtration, oven dry, roasting promptly get Y and Beta ratio be 4: 1, micropore mutually relative amount be 27wt%, the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41, this sample called after D.The specific area of this sample is 710m
2/ g, pore volume are 0.83ml/g, and average pore size is 4.4nm.
The physico-chemical property of Y-Beta/MCM-41 composite molecular screen sample is seen table 1.
Embodiment 5
With two microporous-mesoporous composite molecular sieve A 18g, amorphous aluminum silicide (SiO
2Mass content 34%, pore volume 0.95ml/g, specific area 380m
2/ g) 43.2g, macroporous aluminium oxide (pore volume 0.94ml/g, specific area 385m
2/ g) 36g, sesbania powder 3.6g mix and grind 30min, and (mol ratio of nitric acid, water and little porous aluminum oxide is 0.3: 5: 1, aperture aluminium oxide pore volume 0.42ml/g, specific area 230m by the binding agent of rare nitric acid, little porous aluminum oxide and water preparation to add 120g then
2/ g) mix, continue to roll to being extruded into paste, extrusion is extruded bar at 120 ℃ of dry 4h, and 550 ℃ of roasting 8h of dried bar temperature programming get carrier.Carrier is total to maceration extract (WO with tungstenic nickel phosphorus
3Concentration 54.1g/100ml, NiO concentration 10.8g/100ml, P
2O
5Concentration 3.03g/100ml) behind the room temperature dipping 2h, 120 ℃ of dry 4h, 510 ℃ of roasting 8h of temperature programming make catalyst I.
The percentage by weight of each composition is in the catalyst I: WO
324.5wt%, NiO 6.3wt%, P
2O
52.2wt%, SiO
226.1wt%, Al
2O
339.2wt%.Catalyst I specific area 248m
2/ g, pore volume 0.42ml/g.
Embodiment 6
With two microporous-mesoporous composite molecular sieve B 56g, amorphous aluminum silicide (SiO
2Mass content 34%, pore volume 0.95ml/g, specific area 380m
2/ g) 84g, macroporous aluminium oxide (pore volume 0.94ml/g, specific area 385m
2/ g) 24g, sesbania powder 6g mix and grind 30min, and (mol ratio of nitric acid, water and little porous aluminum oxide is 0.3: 5: 1, aperture aluminium oxide pore volume 0.42ml/g, specific area 230m by the binding agent of rare nitric acid, little porous aluminum oxide and water preparation to add 216g then
2/ g) mix, continue to roll to being extruded into paste, extrusion is extruded bar at 120 ℃ of dry 4h, and 550 ℃ of roasting 8h of dried strip temperature programming get carrier.Carrier is total to maceration extract (WO with tungstenic nickel phosphorus
3Concentration 54.1g/100ml, NiO concentration 10.8g/100ml, P
2O
5Concentration 3.03g/100ml) behind the room temperature dipping 2h, 120 ℃ of dry 4h, 510 ℃ of roasting 8h of temperature programming make catalyst I I.
The percentage by weight of each composition is among the catalyst I I: WO
325.9wt%, NiO 6.1wt%, P
2O
51.8wt%, SiO
225.4wt%, Al
2O
338.2wt%.Catalyst I I specific area 248m
2/ g, pore volume 0.32ml/g.
Embodiment 7
With two microporous-mesoporous composite molecular sieve C 20g, amorphous aluminum silicide (SiO
2Mass content 34%, pore volume 0.95ml/g, specific area 380m
2/ g) 55g, macroporous aluminium oxide (pore volume 0.94ml/g, specific area 385m
2/ g) 10g and sesbania powder 3g mix and grind 30min, and (mol ratio of nitric acid, water and little porous aluminum oxide is 0.3: 5: 1, aperture aluminium oxide pore volume 0.42ml/g, specific area 230m by the binding agent of rare nitric acid, little porous aluminum oxide and water preparation to add 100g then
2/ g) mix, continue to roll to being extruded into paste, extrusion is extruded bar at 120 ℃ of dry 4h, and 550 ℃ of roasting 8h of dried strip temperature programming get carrier.Carrier is total to maceration extract (WO with tungstenic nickel phosphorus
3Concentration 54.1g/100ml, NiO concentration 10.8g/100ml, P
2O
5Concentration 3.03g/100ml) behind the room temperature dipping 2h, 120 ℃ of dry 4h, 510 ℃ of roasting 8h of temperature programming make catalyst I II.
The percentage by weight of each composition is among the catalyst I II: WO
325.3wt%, NiO 5.3wt%, P
2O
52.1wt%, SiO
226.4wt%, Al
2O
339.5wt%.The specific area 241m of catalyst I II
2/ g, pore volume 0.36ml/g.
Embodiment 8
With two microporous-mesoporous composite molecular sieve D 20g, amorphous aluminum silicide (SiO
2Mass content 34%, pore volume 0.95ml/g, specific area 380m
2/ g) 120g, macroporous aluminium oxide (pore volume 0.94ml/g, specific area 385m
2/ g) 40g, sesbania powder 6g mix and grind 30min, and (mol ratio of nitric acid, water and little porous aluminum oxide is 0.3: 5: 1, aperture aluminium oxide pore volume 0.42ml/g, specific area 230m by the binding agent of rare nitric acid, little porous aluminum oxide and water preparation to add 206g then
2/ g) mix, continue to roll to being extruded into paste, extrusion is extruded bar at 120 ℃ of dry 4h, and 550 ℃ of roasting 8h of dried bar temperature programming get carrier.Carrier is total to maceration extract (WO with tungstenic nickel phosphorus
3Concentration 54.1g/100ml, NiO concentration 10.8g/100ml, P
2O
5Concentration 3.03g/100ml) behind the room temperature dipping 2h, 120 ℃ of dry 4h, 510 ℃ of roasting 8h of temperature programming make catalyst I V.
The percentage by weight of each composition is among the catalyst I V: WO
324.8wt%, NiO 6.0wt%, P
2O
52.1wt%, SiO
225.7wt%, Al
2O
337.5wt%.Catalyst I V specific area 235m
2/ g, pore volume 0.35ml/g.
The physico-chemical property of each hydrocracking catalyst sample is seen table 2.
Comparative example
Catalyst V is a kind of industrialized hydrocracking catalyst.The main acidic components of this catalyst are a kind of Modified Zeolite Y and modification Beta type molecular sieve, and its main physico-chemical property is: WO
327.5wt%, NiO 7.4wt%, SiO
225.4wt%, Al
2O
3Surplus.Specific surface area of catalyst 227m
2/ g, pore volume 0.30ml/g.Catalyst V I is the industrialized typical catalyst of another kind.The main acidic components of this catalyst are a kind of modified Y molecular sieve, and its main physico-chemical property is: WO
323.3wt%, NiO 7.1wt%, SiO
230.2wt%, Al
2O
3Surplus.Specific surface area of catalyst 192m
2/ g, pore volume 0.33ml/g.
Embodiment 9
Present embodiment has been introduced the catalyst activity evaluation result.
Get the catalyst I II among the embodiment 7; Adopt one-stage serial technology; With grand celebration decompressed wax oil and wax tailings miscella is raw material (feedstock oil character is seen table 2), on 200ml small stationary bed hydroprocessing evaluating apparatus, estimates, and appreciation condition is: reaction pressure 15.0MPa; Hydrogen to oil volume ratio 1500: 1, volume space velocity 1.5h
-1, in the control feedstock oil＞350 ℃ of distillate conversion ratios are 65%.
The main character of estimating with feedstock oil sees Table 3.
The comparative evaluation result of catalyst I II, V and VI sees table 4.
The physico-chemical property of the two microporous-mesoporous composite molecular sieve samples of table 1 Y-Beta/MCM-41
| Sample number into spectrum | A | B | C | D |
| Y and Beta mass ratio | 1∶2 | 1∶1 | 2∶1 | 4∶1 |
| The relative amount of micropore phase | 0.53 | 0.27 | 0.53 | 0.27 |
| Total acid content (200 ℃), mmol/g | 0.321 | 0.323 | 0.269 | 0.223 |
| L acid amount (200 ℃), mmol/g | 0.185 | 0.176 | 0.134 | 0.108 |
| B acid amount (200 ℃), mmol/g | 0.136 | 0.147 | 0.135 | 0.115 |
| L acid amount/B acid amount | 1.36 | 1.20 | 0.99 | 0.94 |
| Specific area, m 2/g | 867 | 751 | 816 | 710 |
| Pore volume, ml/g | 0.81 | 0.89 | 0.76 | 0.83 |
The physico-chemical property of table 2 hydrocracking catalyst sample
| Sample number into spectrum | I | II | III | IV |
| WO 3，wt％ | 25.3 | 25.9 | 24.5 | 24.8 |
| NiO，wt％ | 5.3 | 6.1 | 6.3 | 6.0 |
| P 2O 5，wt％ | 2.1 | 1.8 | 2.2 | 2.1 |
| SiO 2，wt％ | 26.4 | 25.4 | 26.1 | 25.7 |
| Al 2O 3，wt％ | 39.5 | 38.2 | 39.2 | 37.5 |
| Specific area, m 2/g， | 241 | 248 | 248 | 235 |
| Pore volume, ml/g | 0.36 | 0.32 | 0.42 | 0.35 |
The main character of table 3 feedstock oil
The 200ml hydrogenation comparative evaluation result of table 4 catalyst I II, V and VI
Claims (5)
1. a two microporous-mesoporous composite molecular sieve hydrocracking catalyst is characterized in that: be made up of two microporous-mesoporous composite molecular sieves, amorphous aluminum silicide, macroporous aluminium oxide, binding agent, extrusion aid, VI B family metal oxide, VIII family metal oxide and V A family element oxide;
Two microporous-mesoporous composite molecular sieves are the Y-Beta/MCM-41 composite molecular screen, specific area 600m
2/ g～950m
2/ g, pore volume 0.5ml/g～0.8ml/g, meleic acid amount 0.05mmol/g～0.5mmol/g;
Extrusion aid is the sesbania powder, and VI B family metallic element is W and/or Mo, and VIII family metallic element is Ni and/or Co, and V A family element is a phosphorus;
Catalyst carrier by weight 100%, by 5～30% pairs of microporous-mesoporous composite molecular sieves, 20～50% amorphous aluminum silicides, 5～30% macroporous aluminium oxides, 10～25% binding agents, 2～5% extrusion aids are formed;
By catalyst weight 100%, 10～30% VI B family metal oxide, 5～10% VIII family metal oxides, 0.1～10% V A family element oxide, surplus is a carrier.
2. described pair of microporous-mesoporous composite molecular sieve hydrocracking catalyst of a claim 1 preparation method; It is characterized in that: (1) Y-Beta/MCM-41 composite molecular screen is prepared by following method; With Y and Beta molecular sieve and deionized water mixing stirring; Join then in the mixed solution of softex kw (CTAB) and APES (OP-10) and go; After stirring, drip silicon source and aluminium source solution, the pH value of adjustment system is 8～12; After the system of treating is stable material is transferred to 80 ℃～120 ℃ crystallization 24h～72h in the crystallizing kettle, suction filtration, oven dry, roasting obtain the two microporous-mesoporous composite molecular sieves of Hydrogen Y-Beta/MCM-41 again after the ammonium exchange;
The SiO of described Y molecular sieve
2/ Al
2O
3Mol ratio is 4～20, and specific area is 500m
2/ g～800m
2/ g, pore volume are 0.4ml/g～0.7ml/g; The SiO of Beta molecular sieve
2/ Al
2O
3Mol ratio is 20～50, and specific area is 400m
2/ g～700m
2/ g, pore volume are 0.35ml/g～0.5ml/g;
Proportioning raw materials in molar ratio, CTAB/SiO
2Be 0.10～0.25, CTAB/OP-10 is 5～7, SiO
2/ H
2O is 58～78, Si/Al>=25; Press mass ratio (Y+Beta)/SiO
2Be 0.26～0.80, Y and Beta molecular sieve consumption can carry out the adjusting of arbitrary proportion;
(2) two microporous-mesoporous composite molecular sieves, amorphous aluminum silicide, macroporous aluminium oxide, adhesive and extrusion aid are mixed, extruded moulding, dry, roasting is prepared into carrier;
(3) get the salt and the V A family element preparation maceration extract of VI B family's metallic element and VIII metallic element, flood the carrier of (2) gained, dip time 1h～4h with the maceration extract of gained;
(4) dipping of (3) gained is good carrier strip is dry, obtain the finished product hydrocracking catalyst after the roasting.
3. the preparation method of according to claim 2 pair of microporous-mesoporous composite molecular sieve hydrocracking catalyst is characterized in that: the silicon source is Na
2SiO
3, one or more the mixture in Ludox, silochrom, waterglass, methyl silicate or the ethyl orthosilicate, the aluminium source is NaAlO
2, Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3Or one or more the mixture in the aluminium isopropoxide.
4. the preparation method of according to claim 2 pair of microporous-mesoporous composite molecular sieve hydrocracking catalyst; It is characterized in that: described binding agent is to be mixed and made into by little porous aluminum oxide and acid solution, and the used acid of acid solution comprises one or more mixture of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, oxalic acid etc.
5. the application of described pair of microporous-mesoporous composite molecular sieve hydrocracking catalyst of a claim 1; It is characterized in that: be used for hydrocracking process; Raw material is normal pressure wax oil, decompressed wax oil, wax tailings, deasphalted oil; The material boiling range is 300 ℃～550 ℃, in the raw material＞350 ℃ of cut percent by volume ≮ 60%, nitrogen content 500 μ g/g～2000 μ g/g;
Catalyst need carry out presulfurization and handle before handling heavier feeds, and process conditions are 300 ℃～450 ℃ of reaction temperatures, hydrogen partial pressure 8Mpa～20MPa, and hydrogen to oil volume ratio is 500: 1～2000: 1, volume space velocity 0.5h during liquid
-1～3.0h
-1
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| CN102950020A (en) * | 2012-09-20 | 2013-03-06 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst containing hierarchical pore Beta molecular sieve |
| CN106513035A (en) * | 2016-11-16 | 2017-03-22 | 中国海洋石油总公司 | Preparation method for mesoporous-microporous composite hydroisomerization dewaxing catalyst |
| CN107715923A (en) * | 2013-03-30 | 2018-02-23 | 中国石油化工股份有限公司 | Porous carrier and preparation method and hydrocracking catalyst and method for hydrogen cracking for hydrogenation catalyst |
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| CN102950020A (en) * | 2012-09-20 | 2013-03-06 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst containing hierarchical pore Beta molecular sieve |
| CN102950020B (en) * | 2012-09-20 | 2014-12-03 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst containing hierarchical pore Beta molecular sieve |
| CN107715923A (en) * | 2013-03-30 | 2018-02-23 | 中国石油化工股份有限公司 | Porous carrier and preparation method and hydrocracking catalyst and method for hydrogen cracking for hydrogenation catalyst |
| CN106513035A (en) * | 2016-11-16 | 2017-03-22 | 中国海洋石油总公司 | Preparation method for mesoporous-microporous composite hydroisomerization dewaxing catalyst |
| CN109205636A (en) * | 2017-06-29 | 2019-01-15 | 中国石油天然气股份有限公司 | The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material |
| CN109205636B (en) * | 2017-06-29 | 2020-02-14 | 中国石油天然气股份有限公司 | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material |
| CN110614113A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with rod-shaped mesoporous molecular sieve silica gel composite material as carrier, preparation method and application |
| CN112691650A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Adsorbent and preparation method and application thereof |
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