CN104624227A - Mesoporous-microporous molecular sieve hydrocracking catalyst - Google Patents
Mesoporous-microporous molecular sieve hydrocracking catalyst Download PDFInfo
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- CN104624227A CN104624227A CN201310574627.3A CN201310574627A CN104624227A CN 104624227 A CN104624227 A CN 104624227A CN 201310574627 A CN201310574627 A CN 201310574627A CN 104624227 A CN104624227 A CN 104624227A
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- zeolite
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- -1 organic acid rare earth Chemical class 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 23
- 239000010457 zeolite Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 12
- 150000007530 organic bases Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 9
- 239000002283 diesel fuel Substances 0.000 abstract description 8
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Substances [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a mesoporous-microporous molecular sieve hydrocracking catalyst; the catalyst comprises alumina, an acidic component and hydrogenation active metal, wherein the acidic component comprises a USY molecular sieve with ultralow sodium oxide and potassium oxide contents and a modified ZSM-5 molecular sieve, and the modification method of the modified ZSM-5 molecular sieve comprises the steps of firstly treating ZSM-5 with mixed alkali, then treating a sample after treatment and roasting with an organic acid rare earth solution, and finally filtering, washing and drying to obtain a modified sample; the ZSM-5 molecular sieve of the catalyst maintains a micropore structure to the maximum extent, increases the specific surface area and reduces the damage degree to a framework while manufacturing mesopores, and the catalyst can be used for producing tail oil, heavy naphtha and diesel oil and has the characteristics of high total yield of the tail oil and the heavy naphtha, low condensation point of the diesel oil and low BMCI value of the tail oil.
Description
Technical field
The present invention relates to a kind of mesoporous-micro porous molecular sieve hydrocracking catalyst.Catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and the composite modified ZSM-5 molecular sieve of one, belong to catalyst technical field.
Background technology
ZSM-5 type zeolite molecular sieve is widely used in petroleum refining and petrochemical industry as a good shape-selective catalyst, there is two-dimentional ten-ring pore passage structure, its composition silica alumina ratio can by 10 to total silicon, surface acidic strength and the advantages such as controllable that distribute, become and have the molecular sieve catalyst that height selects shape production light olefin.But micropore ZSM-5 molecular sieve is when relating to macromolecular reaction, because its duct is less, reactant molecule diffusion is hindered, and macromolecular reaction thing crystal duct extremely difficult to get access reacts or large molecular product diffuses out also more difficult from duct, thus limits its range of application.For catalytic reaction, for accelerating the diffusion of reactant molecule and product molecule, two kinds of measures can be taked: one is synthesizing small-grain molecular sieve, shortening the diffusion path of reactant and product.Two is apertures that post processing modification expands molecular sieve.But at present because small crystal grain molecular sieve easily sinters gathering in catalytic reaction process, and be separated comparatively difficulty, thus limit its application industrially.Post processing study on the modification is comparatively extensive, major part work mainly concentrates on steam or acid treatment dealuminzation, and to carry out alkali treatment to molecular sieve be a more novel processing method, passes through basic treatment, optionally deviating from framework silicon, is the microporous mesoporous a kind of effective method of preparation.And adopt mixed base process can retain microcellular structure to greatest extent while generation is mesoporous, and reduce the strong acid quantity of molecular sieve.Compared with inorganic base, the modification rate of organic base to molecular sieve is slower and gentle, has controllability, and can play the effect of duct growth regulator.In numerous after-treatment modification method, its treatment effect is obvious, simple to operate, does not need special installation, with low cost, has a extensive future.
The patent CN101428817A sodium hydroxide solution of 0.1 ~ 5mmol/L processes ZSM-5 molecular sieve 10 ~ 48h at 20 ~ 90 DEG C, and obtain the large aperture ZSM-5 zeolite that diameter is 160 ~ 190nm, its mesopore surface area reaches as high as 217m
2/ g, but microcellular structure is subject to very big destruction, and micropore specific surface only has 141.3m
2/ g.
Patent CN1530322A in 50 ~ 100 DEG C of process ZSM-51 ~ 7h, the highest obtains 250m with the aqueous slkali of 0.1 ~ 0.5mol/L
2the mesopore surface area of/g, but its microcellular structure is also the more serious of destruction.
Masaru Ogura etc. adopt the sodium hydroxide solution process ZSM-5 zeolite 5 ~ 300min of 0.05 ~ 0.2mol/L in Applied Catalysis A:General 219 (2001) 33 – 43, find that the ZSM-5 mesopore surface area of 0.2mol/L naoh treatment is by 6.6m
2/ g is increased to 115.4m
2/ g, micropore specific area is then from 296.4m
2/ g is reduced to 205m
2/ g.Although micropore specific area retains more, mesoporous content is also lower.
Barbara Gil etc. process ZSM-5 zeolite 1h with the sodium hydroxide solution of 0.1 ~ 1mol/L at 80 DEG C in Catalysis Today 152 (2010) 24 – 32, find that the ZSM-5 mesopore surface area of 0.5mol/L naoh treatment is by 67m
2/ g is increased to 211m
2/ g, micropore specific area is then from 288m
2/ g is reduced to 220m
2/ g, when concentration is increased to 1mol/L, micropore, mesopore surface area all decline more, and degree of crystallinity also sharply declines.
Johan C.Groen etc. adopts two step post treatment methods in Microporous and Mesoporous Materials87 (2005) 153 – 161, first at 65 DEG C, 30min is processed with 0.2mol/L NaOH, and then steam 873K process 5h, the sample mesopore surface area after process is by 40m
2/ g is increased to 230m
2/ g, micropore specific area is then from 390m
2/ g is reduced to 235m
2/ g.
Christian Fernandez etc. uses NaOH and hydrochloric acid soda acid mixed processing to prepare multi-stage porous ZSM-5 molecular sieve in Chem.Eur.J.16 (2010) 6224 – 6233.First adopt 0.2mol/L sodium hydroxide solution to process 30min at 65 DEG C, and then at 70 DEG C, process 6h by the hydrochloric acid solution of 0.1mol/L, the sample mesopore surface area after process is by 62m
2/ g is increased to 275m
2/ g, micropore specific area is then from 395m
2/ g is reduced to 298m
2/ g.
Sonia Abello etc. uses 1mol/L tetrapropyl oxyammonia (TPAOH) or tetrabutylammonium hydroxide amine (TBAOH) at 65 ~ 85 DEG C, process 0.5 ~ 8h in Applied Catalysis A:General364 (2009) 191 – 198, between finding when treated when 5h, mesopore surface area is by 60m
2/ g is increased to 180m
2/ g, starts to decline afterwards.And contrasting the NaOH process of 2mol/L, the NaOH of 2mol/L processes 30min at identical conditions, and mesopore surface area is by 60m
2/ g is increased to 277m
2/ g, but compared with organic amine process, inorganic base is comparatively large to the destructiveness of framework of molecular sieve, causes degree of crystallinity obviously to reduce.
Summary of the invention
The ZSM-5 molecular sieve used in catalyst of the present invention is for current technology, namely the simple inorganic base that uses destroys comparatively large to framework of molecular sieve and is difficult to control, simple use organic base cost is higher, the problems such as reaction rate is slower, invented one aim to provide higher mesopore surface area while retain microcellular structure to greatest extent, and alleviate the method for modifying of the destruction to framework of molecular sieve.
The method of modifying of the ZSM-5 molecular sieve used in catalyst of the present invention mainly comprises alkali treatment and acid treatment.Alkali treatment process uses organic base and the process of inorganic base mixed base, in conjunction with inorganic base treatment effect obviously and the mesoporous ZSM-5 that obtains of organic base process without the need to carrying out ammonium ion exchange again, and the speed of desiliconization is slower than conventional alkali treatment method, the advantages such as easy control, overcome the degree of crystallinity of inorganic base processing procedure Middle molecule sieve, acid amount, the difference such as heat endurance are larger, organic base processing cost is high, desiliconization selective poor, have a large amount of aluminium in process and be dissolved in the medium shortcoming of organic alkali solution, preparation ZSM-5 sample generate mesoporous while retain microcellular structure to greatest extent, and the destruction alleviated framework of molecular sieve, reduce the strong acid quantity of molecular sieve, acid treatment process is then remove the indefiniteness aluminium in zeolite crystal, thus reaches the object in dredging duct.
One of the present invention is mesoporous-micro porous molecular sieve hydrocracking catalyst preparation method.Catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and the composite modified ZSM-5 molecular sieve of one.Hydrocracking catalyst prepared by this method, can produce tail oil, heavy naphtha and diesel oil flexibly, and catalyst has tail oil and heavy naphtha total recovery is high, condensation point of diesel oil is low and tail oil BMCI value is low feature.
The method of modifying of the ZSM-5 molecular sieve used in catalyst, comprises the following steps:
(1) prepare the organic base Oh (Organic hydroxides) of variable concentrations and the mixed solution of inorganic base Inh (Inorganic hydroxides) (different Oh/Inh), keep total OH
-concentration is in (0.05 ~ 0.5mol/L) scope, and the value of Oh/Inh can change in 0.1 ~ 1 scope;
(2) get ZSM-5 zeolite, join in mixed ammonium/alkali solutions prepared by step (1) by the solid-to-liquid ratio of 10 ~ 100mL/g, at 25 ~ 95 DEG C, stir 10 ~ 420min;
(3) sample prepared by step (2) is carried out through frozen water sudden cold, filter, dry, roasting;
(4) sample that step (3) obtains is mixed according to a certain percentage with organic acid earth solution, at room temperature stir, then stir process 5 ~ 300min at 25 ~ 95 DEG C;
(5) product step (4) obtained after filtration, wash, be drying to obtain the modified ZSM-5 zeolite of process.
According to ZSM-5 method of modifying of the present invention, wherein step (1) described mixed base is the mixed solution of organic base tetramethyl oxyammonia (TMAOH) or hexamethylene diamine and inorganic base KOH or NaOH; Add the OH of aqueous slkali
-concentration is that 0.05 ~ 0.5mol/L, Oh/Inh molar ratio can change in 0.1 ~ 1 scope.
The solid-to-liquid ratio of step (2) described mixed ammonium/alkali solutions and ZSM-5 is 10 ~ 100mL/g, preferably 20 ~ 80mL/g; Treatment temperature is 25 ~ 95 DEG C, preferably 35 ~ 80 DEG C; Processing time is 10 ~ 480min, preferably 30 ~ 300min.
Organic acid earth solution described in step (4) is citric acid 0.001 ~ 0.1 interpolation lanthanum nitrate in molar ratio, and citric acid concentration is 0.05 ~ 1mol/L, and treatment temperature is 25 ~ 95 DEG C, preferably 35 ~ 80 DEG C; Processing time is 5 ~ 360min, preferably 1 ~ 4h.
The ZSM-5 zeolite of step (5) gained has following character: the XRD feature spectrogram with ZSM-5; At N
2there is micropore and mesoporous composite bore diameter in the aperture measured by adsorption-desorption, mesoporous high with micropore specific area.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the ZSM-5 modified zeolite that embodiment 1 obtains
Fig. 2 is the graph of pore diameter distribution of the ZSM-5 modified zeolite that embodiment 1 obtains
Detailed description of the invention
In the inventive method, the crystal structure of modified ZSM-5 zeolite sample adopts Rigaku D/max-2500 type X-ray diffractometer of science.Condition of work is: graphite monochromator, Cu K alpha ray (λ=0.154nm), tube current 40mA, tube voltage 40kV, and walk wide 0.02 °, sweep speed is 12 °/min, repeatable accuracy 1/1000 °.Wideangle scanning scope 3 °≤2 θ≤80 °.
The porous of sample, at Kang Ta instrument company of U.S. Quantachrome Instruments NOVA 2000e high speed specific surface and lacunarity analysis instrument, carries out nitrogen adsorption/detachment assays under 77K liquid nitrogen temperature, image data point.Before test, all samples is Fruit storage 5-10 hour at 200 DEG C all; The calculating of specific surface is obtained by multiple spot BET theory calculate, coefficient correlation (Correlation Cofficient) >0.9999; Pore-size distribution adopts Barret-Joyner-Halenda (BJH) method or Density function Theory(DFT) calculate, the pore passage structure of sample is also analyzed by the theory of being correlated with.
Give detailed description below by specific embodiment to the ZSM-5 molecular sieve method of modifying used in invention and method for preparing catalyst, but be not limited to embodiment.
The raw material ZSM-5 that the present invention uses is from Shenneng Science-Technology Co., Ltd., Tianjin, and its silica alumina ratio is 38, and specific area is 364m
2/ g, micropore specific area 277m
2/ g, mesopore surface area 87m
2/ g.The acid used, alkali and solvent are analyzes pure chemistry reagent.
Embodiment 1
Get TMAOH and the KOH (TMA that 1g ZSM-5 zeolite adds 50mL 0.2mol/L
+/ OH
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-1.
As seen from Figure 1, BA-1 sample has the XRD feature spectrogram of ZSM-5, still keeps that good ZSM-5's is zeolite structured.As seen from Figure 2, after modification, exist significantly mesoporous in ZSM-5 zeolite, aperture is concentrated, and most probable pore size is 3.84nm.
Embodiment 2
Get TMAOH and the NaOH (TMA that 1g ZSM-5 zeolite adds 50mL0.2mol/L
+/ OH
-=6) in, 30min is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-2.
Embodiment 3
Get TMAOH and the KOH (TMA that 1g ZSM-5 zeolite adds 50mL0.2mol/L
+/ OH
-=2) in, 300min is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-3.
Embodiment 4
Get hexamethylene diamine and KOH (hexamethylene diamine/OH that 1g ZSM-5 zeolite adds 50mL0.2mol/L
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-4.
Embodiment 5
Get hexamethylene diamine and NaOH (hexamethylene diamine/OH that 1g ZSM-5 zeolite adds 50mL 0.2mol/L
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-5.
Comparative example 1
Getting 1g ZSM-5 zeolite adds in the NaOH of 50mL 0.2mol/L, stirs 4h at 80 DEG C, filters, and deionized water washing is to neutral, and it is BA-6 that gained solid dries gained sample number into spectrum at 110 DEG C.
Comparative example 2
Get 1g ZSM-5 zeolite and add 80 DEG C of process 4h in the citric acid solution of 50mL 0.20mol/L, filtration, deionized water washing are to neutral, and it is BA-7 that gained solid dries gained sample number into spectrum at 110 DEG C.
Comparative example 3
Getting 1g ZSM-5 zeolite adds in the TMAOH of 50mL 0.2mol/L, stirs 5h at 65 DEG C, filters, and deionized water washing is to neutral, and gained solid is dried at 110 DEG C, and gained sample number into spectrum is BA-8.
The pore structure character of embodiment 1 ~ 5 and the ZSM-5 modified zeolite sample prepared by comparative example 1 ~ 3 lists in table 1.The pore structure character of sample involved by table 1 embodiment and comparative example
Embodiment 5
35g USY molecular sieve, 5g modified zsm-5 zeolite (BA-1), 40g macroporous aluminium oxide, 20 little porous aluminum oxides and 5.2g sesbania powder are put into roller, mixed grind 30min, the mixed solution of 10g red fuming nitric acid (RFNA) and 100g water is added after mixing, be extruded into the cylindrical bar of 1.5mm, 120 DEG C of dry 4hr, in 550 DEG C of air atmospheres, roasting 5hr obtains catalyst carrier.The solution room temperature immersion 1hr of 100ml water is dissolved in again, 120 DEG C of dry 4hr, roasting 5hr in 500 DEG C of air atmospheres, obtained hydrocracking catalyst of the present invention with 44g nickel nitrate, 79g ammonium metatungstate.
Comparative example 4
Comparative example 4 catalyst is commercially available similar catalyst.Main component contains Y molecular sieve, amorphous aluminum silicide and alumina composition etc. by analysis, and metal component is tungsten and nickel.
Table 2 feedstock property
Table 3 catalyst 200ml hydrogenation plant evaluating data
| Catalyst | Embodiment 5 | Comparative example 4 |
| Feedstock oil | VGO+CGO | VGO+CGO |
| Volume space velocity during liquid, h -1 | 2.5 | 2.5 |
| Hydrogen to oil volume ratio | 800:1 | 800:1 |
| Reaction pressure, MPa | 9.0 | 9.0 |
| Reaction temperature, DEG C | 383 | 384 |
| Product yield, wt.% | 98.6 | 98.6 |
| Light naphthar HK ~ 65 DEG C | 3.33 | 5.03 |
| Heavy naphtha 65 DEG C ~ 165 DEG C | 25.77 | 20.07 |
| Diesel oil 165 DEG C ~ 350 DEG C | 34.70 | 37.76 |
| Condensation point of diesel oil, DEG C | <-45 | -16 |
| Tail oil > 350 DEG C | 37.20 | 37.14 |
| BMCI value | 7 | 12 |
As can be seen from Table 3, the tail oil in embodiment 5 and heavy naphtha yield are all higher than comparative example 4, and condensation point of diesel oil and tail oil BMCI value are all better than comparative example 4.Catalyst has tail oil and heavy naphtha total recovery is high, condensation point of diesel oil is low and tail oil BMCI value is low feature.
Claims (3)
1. mesoporous-micro porous molecular sieve hydrocracking catalyst, catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and a kind of modified zsm-5 zeolite; It is characterized in that: described USY molecular sieve sodium oxide molybdena and potassium oxide total content are 0.01 ~ 0.03wt.%; Described ZSM-5 molecular sieve is through following composite modifying method modification:
(1) prepare the organic base of variable concentrations and the mixed solution of inorganic base, keep total OH
-concentration is in the scope of 0.05 ~ 0.5mol/L, and the molar ratio of organic base/inorganic base changes in 0.1 ~ 1 scope;
(2) get ZSM-5 zeolite, join in mixed ammonium/alkali solutions prepared by step (1) by the solid-to-liquid ratio of 10 ~ 100ml/g, at 25 ~ 95 DEG C, stir 10 ~ 480min;
(3) sample prepared by step (2) is carried out through frozen water sudden cold, filter, dry, roasting;
(4) sample that step (3) obtains is mixed with organic acid earth solution, at room temperature stir, then stir process 5 ~ 360min at 25 ~ 95 DEG C; Described organic acid earth solution is citric acid 0.001 ~ 0.1 interpolation lanthanum nitrate in molar ratio, and citric acid is 0.05 ~ 1mol/L;
(5) product step (4) obtained after filtration, wash, be drying to obtain the modified ZSM-5 zeolite of process.
2. according to according to claim 1 mesoporous-micro porous molecular sieve hydrocracking catalyst, it is characterized in that: step (1) described mixed base is the mixed solution of organic base and inorganic base, wherein organic base is tetramethyl oxyammonia or hexamethylene diamine, and inorganic base is KOH or NaOH.
3. according to according to claim 1 mesoporous-micro porous molecular sieve hydrocracking catalyst, it is characterized in that: the organic acid earth solution described in step (4) is the mixed solution of citric acid and lanthanum nitrate.
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