CN114471675A - Modified ZSM-5 molecular sieve for hydrodewaxing and preparation method thereof - Google Patents
Modified ZSM-5 molecular sieve for hydrodewaxing and preparation method thereof Download PDFInfo
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- CN114471675A CN114471675A CN202011161998.5A CN202011161998A CN114471675A CN 114471675 A CN114471675 A CN 114471675A CN 202011161998 A CN202011161998 A CN 202011161998A CN 114471675 A CN114471675 A CN 114471675A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- 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 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 82
- 238000001035 drying Methods 0.000 claims abstract description 48
- 238000011282 treatment Methods 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 239000007853 buffer solution Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 238000005406 washing Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 31
- 238000010335 hydrothermal treatment Methods 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- HJZJUZPJFRJXLT-UHFFFAOYSA-N diazanium oxalate oxalic acid Chemical compound [NH4+].[NH4+].OC(=O)C(O)=O.[O-]C(=O)C([O-])=O HJZJUZPJFRJXLT-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000010306 acid treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 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 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- NTYCOXGJEIKLMU-UHFFFAOYSA-N [Na].S=O Chemical compound [Na].S=O NTYCOXGJEIKLMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 239000013065 commercial product Substances 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 230000000881 depressing effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 description 93
- 238000000967 suction filtration Methods 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- -1 silicate ester Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a modified ZSM-5 molecular sieve for hydrodewaxing and a preparation method and application thereof. The method comprises the following steps: (1) carrying out desiliconization treatment on the ZSM-5 molecular sieve; (2) carrying out dealuminization treatment on the material in the step (1); (3) dipping the material in the step (2) by adopting an acidic buffer solution; (4) and (4) loading amino silicone oil on the material obtained in the step (3), and drying and roasting to obtain the modified ZSM-5 molecular sieve finally used for hydrodewaxing. The molecular sieve prepared by the method has large sieve pore volume and low acid content, can effectively reduce side reactions such as cracking of cyclic hydrocarbon/isoparaffin and secondary cracking of straight-chain alkane in the hydrodewaxing process, and promotes the hydrogenation ring opening of polycyclic aromatic hydrocarbon, and the preparation method thereof.
Description
Technical Field
The invention relates to a modified ZSM-5 molecular sieve for hydrodewaxing and a preparation method thereof, in particular to a modified ZSM-5 molecular sieve which has large pore volume and low acid content, can effectively reduce side reactions such as cracking of cyclic hydrocarbon/isoparaffin and secondary cracking of straight-chain paraffin and the like in the hydrodewaxing process and can promote the hydrogenation ring opening of polycyclic aromatic hydrocarbon and a preparation method thereof.
Background
ZSM-5 is a molecular sieve with a three-dimensional framework structure, and the framework structure comprises two pore channels which are connected in an interlaced way: (1) a straight channel orthogonal to the XY plane, wherein an orifice is formed by an elliptic ten-membered ring, and the aperture is 0.58nm multiplied by 0.52 nm; (2) sinusoidal "Z" shaped channels parallel to the XY plane with pore sizes of 0.53nm by 0.56 nm. This pore structure characteristic gives it shape selective catalytic properties. Therefore, the ZSM-5 molecular sieve has very wide application in the fields of toluene methanol alkylation, isomerization dewaxing, hydrodewaxing and the like. The toluene methanol alkylation reaction mainly utilizes that the molecular dynamics diameter of p-xylene is equivalent to that of a ZSM-5 molecular sieve pore passage, and the diffusion rate is faster than that of o-xylene and m-xylene, thereby realizing the selectivity of p-xylene. The hydrodewaxing reaction utilizes that the molecular dynamics size of most cyclic hydrocarbons and isoparaffins is larger than that of the pore passages of the ZSM-5 molecular sieve, so that the pore passages cannot enter the ZSM-5 molecular sieve for reaction, and the selective cracking of the chain hydrocarbon with poor low-temperature fluidity is realized.
In order to improve the catalytic performance of the ZSM-5 molecular sieve, technicians develop a series of modification methods of the ZSM-5 molecular sieve.
CN101259424B discloses a preparation method of a binderless ZSM-5 zeolite catalyst for shape selective disproportionation of toluene, which mainly takes ZSM-5 zeolite as a main active component and is prepared by a series of modification methods such as molding, template-free hydrothermal crystallization, acid cleaning, dealumination and silicon supplementation, silicate ester chemical liquid phase deposition treatment and the like. However, in the process of dealuminization and silicon supplement, a large amount of non-framework aluminum is generated to block the pore channels, and the subsequent liquid phase deposition treatment is added to further block the pore channels, so that the diffusion of reactants and products is influenced.
CN101380591A discloses a method for preparing an alkali-treated modified ZSM-5 zeolite toluene disproportionation catalyst, which is to remove part of silicon on a framework by alkali to cause partial framework local collapse and generate partial mesopores. Then washing with organic acid, drying the catalyst, carrying out chemical liquid phase deposition modification by using cyclohexane solution of ethyl orthosilicate, drying and roasting to obtain the catalyst, wherein the obtained catalyst is particularly suitable for preparing benzene and paraxylene by shape-selective disproportionation of toluene, and can obviously enhance the conversion rate of the toluene.
The selectivity of the ZSM-5 molecular sieve in the toluene-methanol disproportionation reaction can be improved through subsequent modification, but when the catalyst is applied to the hydrodewaxing reaction, the modes of acid treatment, alkali treatment and the like not only can play a role in pore expansion, but also the pore expansion can possibly cause beneficial components in diesel fraction, namely isoparaffin and/or monocyclic aromatic hydrocarbon to enter the pore channel and even react, and the brought non-framework aluminum can block the pore channel to a certain extent, so that the diffusion of cracking products is hindered, secondary cracking reaction is caused, and the yield and the quality of target products are reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified ZSM-5 molecular sieve for hydrodewaxing and a preparation method thereof, wherein the molecular sieve prepared by the method has large sieve pore volume and low acid content, can effectively reduce side reactions such as cracking of cyclic hydrocarbon/isoparaffin and secondary cracking of straight-chain alkane in the hydrodewaxing process, and promotes the ring opening of polycyclic aromatic hydrocarbon hydrogenation and the preparation method thereof.
A preparation method of a modified ZSM-5 molecular sieve for hydrodewaxing comprises the following steps:
(1) carrying out silicon dissolving treatment on the ZSM-5 molecular sieve;
(2) carrying out dealuminization treatment on the material obtained in the step (1);
(3) dipping the material in the step (2) by adopting an acidic buffer solution;
(4) the amino silicone oil is loaded on the material in the step (3), and the amino silicone oil is dried and roasted to obtain the amino silicone oil which is finally used for the hydrogen
Pour point depressing modified ZSM-5 molecular sieve.
In the method of the present invention, the ZSM-5 molecular sieve used in step (1) may be commercially available or may be prepared according to the following method
The preparation method comprises the following steps. For example, the following method is adopted for preparation: adding a certain amount of sodium oxysulfide, deionized water, sodium metaaluminate, silica gel and a template agent (TPA)2O) mixing, wherein the molar ratio of the materials is as follows: (25-300) SiO2：1Al2O3：TPA2O：（0.01~10）Na2O：（100~1100）H2O; transferring the mixed materials into a stainless steel crystallization kettle, and crystallizing at a certain temperature; after crystallization is finished, washing the mixture product with deionized water until the pH value is 7-8; and drying the obtained sample at 110 ℃ and grinding.
In the method, the desiliconization treatment in the step (1) can adopt one or more of NaOH, quaternary ammonium salt and NaOH treatment under the protection of quaternary ammonium salt.
In the method, the desiliconization treatment in the step (1) adopts alkali treatment, and the alkali treatment process comprises the following steps: ZSM-5 molecular sieve is placed in OH-Stirring for 0.5-2 h in 0.1-1.0 mol/L aqueous alkali, wherein the volume ratio of liquid to solid is (6-10) in ml/g: 1, filtering after treatment, and repeating the process for 2-4 times; and then washing the obtained product for 1-5 times by using deionized water until the content of alkali metal ions is lower than 0.1wt%, and drying to obtain the alkali-modified ZSM-5 molecular sieve. The alkali is one or more of NaOH, KOH and the like. The treatment temperature is 40-70 ℃. The water washing temperature is 40-70 ℃. The liquid-solid ratio in ml/g in the treatment process is (8-12): 1, and the liquid-solid ratio in ml/g in the water washing process is (8-12): 1.
In the method, the dealuminization treatment in the step (2) adopts acid treatment, and the acid treatment process comprises the following steps: ZSM-5 molecular sieve in H+Dipping in an acid solution with the content of 0.1-1.0 mol/L for 0.5-2 h, filtering after treatment, and repeating the process for 2-4 times; and then washing the obtained product for 1-5 times by using deionized water until the content of acid radical ions is lower than 0.1wt%, and drying to obtain the acid-treated ZSM-5 molecular sieve. The acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, etc. The dipping treatment temperature is 40-70 ℃. The water washing temperature is 40-70 ℃. The liquid-solid ratio in ml/g in the dipping treatment process is (8-12): 1, the liquid-solid ratio in ml/g in the water washing process is (8-12): 1.
in the method, the dealuminization treatment in the step (2) adopts hydrothermal treatment, and the hydrothermal treatment process comprises the following steps: and carrying out hydrothermal treatment on the ZSM-5 molecular sieve at the temperature of 400-700 ℃ for 0.5-5 h under the steam pressure of 0.05-0.5 MPa to obtain the hydrothermally treated ZSM-5 molecular sieve.
In the embodiment of the invention, the ZSM-5 molecular sieve is subjected to desiliconization and dealuminization by alkali treatment, acid treatment and hydrothermal treatment in sequence, and the acidity and non-framework aluminum of the molecular sieve are modulated while pore expansion is carried out.
In the method, the pH value of the acidic buffer solution in the step (2) is 5.7-6.4, preferably 5.9-6.2, and the specific process is as follows: soaking the treated molecular sieve in a buffer solution for 0.5-2 h, wherein the volume ratio of liquid to solid is (8-12): 1 in ml/g, the treatment temperature is 40-70 ℃, filtering is carried out after treatment, and the process is repeated for 2-4 times; and then directly drying or drying after washing to obtain the ZSM-5 molecular sieve treated by the acidic buffer solution.
In the method, the acidic buffer solution in the step (2) is any buffer solution with the pH meeting the requirement, and for simplification of the subsequent treatment process, an oxalic acid-ammonium oxalate buffer solution is adopted in the embodiment, and the buffer solution containing components which are not easy to calcine is selected for treatment, and then the buffer solution is washed for 2-3 times by deionized water.
In the method of the present invention, the supported amino silicone oil described in step (3) is impregnated by an impregnation method, and the impregnation can be performed by an equal volume or an over-volume impregnation, and preferably by an equal volume.
In the method, the amino value of the amino silicone oil in the step (3) is 0.6-1.0. In the embodiment of the invention, 0.02-0.10 wt%, preferably 0.04-0.06 wt% of emulsified liquid containing amino silicon oil is used for isovolumic impregnation of the material prepared in the step (2), the solvent is deionized water, and the isovolumic impregnation time is 5-10 hours.
In the method, the drying temperature in the step (3) is 100-150 ℃, and the drying time is 2-4 h; the roasting temperature is 550 ℃; the roasting time is 3-5 h.
The ZSM-5 molecular sieve prepared by the method has the specific surface area of 350-500 m2Per g, preferably 400 to 450m2Per g, pore volume of 0.38-0.50 cm3A/g, preferably 0.40 to 0.45cm3The total acid content is 1.6-2.7 mmol/g, preferably 2.0-2.5 mmol/g, the weak acid content is 0.8-1.4 mmol/g, preferably 1.0-1.2 mmol/g, and the non-skeleton aluminum accounts for the ratio6-12%, preferably 8-10%, and the content of the loaded silicon oxide is 0.02-0.07 wt%, preferably 0.04-0.06 wt%.
The ZSM-5 molecular sieve has the reaction pressure of 6.0MPa, the hydrogen-oil volume ratio of 500:1 and the volume space velocity of 10h -1And under the condition that the reaction temperature is 340 ℃, the ring opening rate of the modified ZSM molecular sieve to decalin is as follows: 50-70% of n-hexadecane, and the secondary cracking rate of the n-hexadecane is 1-6%.
A hydrodewaxing method is characterized in that a diesel raw material reacts under the action of a hydrodewaxing catalyst, wherein the hydrodewaxing catalyst contains a ZSM-5 molecular sieve prepared by the method, and the mass content of polycyclic aromatic hydrocarbons in the raw material oil is higher than 40%, and is preferably 55-75%.
In the above hydrodewaxing method, the hydrodewaxing reaction conditions are as follows: the reaction pressure is 5.0-8.0MPa, the volume ratio of hydrogen to oil is 400:1-600:1, the volume space velocity is 8-112 h-1, and the reaction temperature is 280-400 ℃.
Compared with the prior art, the invention provides a modified ZSM-5 molecular sieve, which generates skeleton collapse through hole expansion treatment to form a large number of secondary mesopores, removes partial non-skeleton aluminum in pore channels by adopting a buffer solution with weaker acidity, ensures that the molecular sieve has a more smooth pore channel structure and a certain amount of weak acid sites in the pore channels, adopts amino silicone oil to partially mask the outer surface of the molecular sieve and the acidity in the mesopores, ensures that the amino silicone oil is preferentially adsorbed at strong acid and medium acid centers due to the alkalinity of the amino silicone oil, controls the using amount of the amino silicone oil, can reserve the weak acid center on the outer surface of the molecular sieve, ensures that polycyclic aromatic hydrocarbon which accounts for more than 40wt% of raw material and is easy to adsorb is subjected to hydrogenation ring-opening on the weak acid sites in the pore and the outer surface so as to improve the quality of diesel oil, and monocyclic hydrocarbon and chain-shaped isomeric hydrocarbon which have higher quality and lower condensation point have poorer adsorption capacity at the weak acid center, but also is difficult to enter the microporous pore canal of the ZSM-5 molecular sieve and is retained in the product. The normal alkane has weaker adsorption capacity relative to the aromatic hydrocarbon and does not dominate in competitive adsorption outside the pore channel, so that the normal alkane enters the microporous pore channel to perform shape-selective cracking reaction to obtain a primary cracking product with a reduced condensation point, and the cracked normal alkane can more quickly diffuse away from the pore channel, thereby reducing secondary cracking and improving the yield of diesel oil.
Detailed Description
The following examples and comparative examples are given to further illustrate the effects and effects of the method of the present invention, but the following examples are not intended to limit the method of the present invention, and the% values referred to in the examples and comparative examples are mass percentages unless otherwise specified.
In the examples of the present invention, the specific surface area and pore volume were determined as follows: the method adopts an ASAP 2420 low-temperature liquid nitrogen physical adsorption instrument manufactured by MICROMERICICS, USA, and the pretreatment temperature is as follows: the pretreatment time is 4h at 300 ℃; the method for measuring the acid content and the acid distribution comprises the following steps: adopting temperature programmed desorption method (NH 3-TPD), pretreating the sample for 1h under He gas flow at 500 deg.C, cooling to below 100 deg.C, adsorbing 0.5% NH3/He to saturation, and removing the physically adsorbed NH by blowing with He gas3Then, the temperature is programmed to 800 ℃ at the temperature rise rate of 10 ℃/min for desorption, and the desorbed NH is3And (5) detecting by a thermal conductivity cell, and blowing the He gas till the end.
In the embodiment of the invention, the method for measuring the ring opening rate of decalin is as follows: decahydronaphthalene is used as a raw material, and the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 800: 1, and the volume airspeed is 0.5h-1And the ratio of ring-opened products is calculated according to the following formula under the condition that the reaction temperature is 350 ℃:
(1-the molar weight of the bicyclic aromatic hydrocarbon and the bicyclic cyclic hydrocarbon in the product/the molar weight of the decahydronaphthalene in the raw material) x 100%;
the method for measuring the secondary cracking rate of the n-hexadecane comprises the following steps:
the product contains C1-C7 mass/n-hexadecane mass × 100%
The measurement conditions are that the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 500:1, and the volume airspeed is 10h -1And the reaction temperature was 340 ℃.
The ZSM-5 involved in the examples and the comparative examples of the invention is a purchased commercial product, and the properties of the ZSM-5 are as follows: specific surface area: 200 to 250 m2Per g, pore volume: 0.20-0.30 cm3/g。
Example 1
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 50 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.1mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.1mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 400 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.4, treating the filter cake at 50 ℃ for 1h and repeating the treatment twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G1 molecular sieve. ZSM-5G1 was characterized and its properties are shown in Table 2.
Example 2
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 50 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.3mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.3mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 450 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.3, treating the filter cake at 50 ℃ for 1h and repeating the treatment twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.08G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G2 molecular sieve. ZSM-5G2 was characterized and its properties are shown in Table 2.
Example 3
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 60 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.3mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.5mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake into 1000mL of deionized water, washing for three times at 50 ℃, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 500 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.2, treating the filter cake at 50 ℃ for 1.5h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G3 molecular sieve. ZSM-5G3 was characterized and its properties are shown in Table 2.
Example 4
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 60 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.3mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.3mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 500 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.1, treating the filter cake at 50 ℃ for 1.5h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G4 molecular sieve. ZSM-5G4 was characterized and its properties are shown in Table 2.
Example 4
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 60 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.3mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.3mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 500 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.1, treating the filter cake at 50 ℃ for 1.5h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G4 molecular sieve. ZSM-5G4 was characterized and its properties are shown in Table 2.
Example 5
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 60 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.5mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.5mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 550 ℃ and 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 6.0, treating the filter cake at 50 ℃ for 2.0h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.07G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G5 molecular sieve. ZSM-5G5 was characterized and its properties are shown in Table 2.
Example 6
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 60 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.7mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.7mol/L for 1h at 50 ℃ and is repeatedly processed twice, and the filtration is carried out; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 550 ℃ and 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 5.9, treating the filter cake at 50 ℃ for 2.0h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.07G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G6 molecular sieve. ZSM-5G6 was characterized and its properties are shown in Table 2.
Example 7
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 70 ℃ in 1000mL of hydrochloric acid solution with the concentration of 0.9mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 0.9mol/L for 1h at 50 ℃ and is repeatedly filtered twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 600 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 5.8, treating the filter cake at 50 ℃ for 3.0h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.09G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G7 molecular sieve. ZSM-5G7 was characterized and its properties are shown in Table 2.
Example 8
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 80 ℃ in 1000mL of hydrochloric acid solution with the concentration of 1.0mol/L and is filtered in a suction way twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the filter cake is placed in 1000mL NaOH solution with the concentration of 1.0mol/L for 1h at 50 ℃ and is repeatedly filtered twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 ℃ for 6h, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 650 ℃ and under the pressure of 0.1MPa for 2h, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with the pH value of 5.7, treating the filter cake at 50 ℃ for 5.0h repeatedly twice, and carrying out suction filtration; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; and drying the filter cake at 120 ℃ for 6h, weighing 64mL amino silicon oil-water solution with the concentration of 0.09G/L, soaking for 24h in an equal volume, drying at 120 ℃ for 6h, taking out, placing in a muffle furnace, raising the temperature to 550 ℃, and roasting for 3h to obtain the ZSM-5G8 molecular sieve. ZSM-5G8 was characterized and its properties are shown in Table 2.
Table 1 examples 2-8 molecular sieve treatment conditions
Table 2 examples 1-8 molecular sieve characterization results
The molecular sieve of the embodiment 1-8 is used for preparing the catalyst, and the preparation process comprises the steps of kneading the molecular sieve, macroporous alumina and a binder, extruding into strips, forming, drying and roasting to obtain a carrier; impregnating the carrier with nickel nitrate impregnation liquid, and then drying and roasting to obtain a catalyst; wherein the mass percent of the molecular sieve is 30wt%, the mass percent of the macroporous alumina is 50wt%, the mass percent of NiO is 10wt%, and the balance is the binder. 10g of the catalyst is put into a fixed bed reactor, and the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 10h -1The hydrodewaxing reaction is carried out at the reaction temperature of 340 ℃,the raw material properties are shown in Table 3, and the product distribution and product properties are shown in Table 4.
TABLE 3 Properties of the feed oils
Table 4 catalyst product distribution and properties prepared from molecular sieves obtained by this approach
Comparative example
According to the traditional molecular sieve modification method, 100g of ZSM-5 raw powder is treated for 1h at 80 ℃ in 1000mL of hydrochloric acid solution with the concentration of 1.0mol/L and is filtered twice; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; drying the filter cake at 120 deg.C for 6h, placing in a hydrothermal treatment kettle, performing hydrothermal treatment at 500 deg.C under 0.1MPa for 2h, and vacuum filtering; placing the obtained filter cake in 1000mL of deionized water, washing for three times at 50 ℃, and then carrying out suction filtration; the obtained ZSM-5G molecular sieve is a cracking component, and is kneaded, extruded and formed with macroporous alumina and a binder, and then dried and roasted to obtain a carrier; impregnating the carrier with nickel nitrate impregnation liquid, and then drying and roasting to obtain a catalyst; wherein the mass percent of ZSM-5G is 30wt%, the mass percent of macroporous alumina is 50wt%, the mass percent of NiO is 10wt%, and the balance is binder. 10g of the catalyst is put into a fixed bed reactor, and the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 10h -1And the reaction temperature is 340 ℃ under the hydrodewaxing condition. The catalyst performance was investigated starting from a mixture of decalin and 1,3, 5-triisopropylbenzene, and n-hexadecane, respectively. The physicochemical properties of the molecular sieves and the cracking rates for the different feedstocks are shown in table 5.
TABLE 5 physical and chemical Properties and catalytic Performance of HZSM-5
Claims (20)
1. A preparation method of a modified ZSM-5 molecular sieve for hydrodewaxing is characterized by comprising the following steps: the method comprises the following steps:
carrying out desiliconization treatment on the ZSM-5 molecular sieve;
carrying out dealuminization treatment on the material obtained in the step (1);
dipping the material in the step (2) by adopting an acidic buffer solution;
the amino silicone oil is loaded on the material in the step (3), and the amino silicone oil is dried and roasted to obtain the amino silicone oil which is finally used for the hydrogen
Pour point depressing modified ZSM-5 molecular sieve.
2. The method of claim 1, wherein: the ZSM-5 molecular sieve in the step (1) is a commercial product or is prepared according to the prior art.
3. The method of claim 1, wherein: the preparation method of the ZSM-5 molecular sieve comprises the following steps: adding a certain amount of sodium oxysulfide, deionized water, sodium metaaluminate, silica gel and a template agent (TPA)2O) mixing, wherein the molar ratio of the materials is as follows: (25-300) SiO2：1Al2O3：TPA2O：（0.01~10）Na2O：（100~1100）H2O; transferring the mixed materials into a stainless steel crystallization kettle, and crystallizing at a certain temperature; after crystallization is finished, washing the mixture product by deionized water until the pH value is 7-8; and drying the obtained sample at 110 ℃ and grinding.
4. The method of claim 1, wherein: in the step (1), one or more of NaOH and quaternary ammonium salt is/are used as a desiliconization reagent in the desiliconization treatment.
5. The method of claim 1, wherein: the desiliconization treatment in the step (1) adopts alkali treatment, and the alkali treatment process is as follows: ZSM-5 molecular sieve is placed in OH-Stirring for 0.5-2 h in 0.1-1.0 mol/L aqueous alkali, wherein the volume ratio of liquid to solid is (6-12) in ml/g: 1, filtering after treatment, and repeating the process for 2-4 times; and then washing the obtained product for 1-5 times by using deionized water until the content of alkali metal ions is lower than 0.1wt%, and drying to obtain the desiliconized ZSM-5 molecular sieve.
6. The method of claim 5, wherein: the alkali is one or more of NaOH and KOH, the treatment temperature is 40-70 ℃, the water washing temperature is 40-70 ℃, the liquid-solid ratio in the treatment process is (8-10): 1 in terms of ml/g, and the liquid-solid ratio in the water washing process is (8-12): 1 in terms of ml/g.
7. The method of claim 1, wherein: in the step (2), the dealuminization treatment adopts acid treatment, and the acid treatment process is as follows: ZSM-5 molecular sieve in H+Dipping in an acid solution with the content of 0.1-1.0 mol/L for 0.5-2 h, filtering after treatment, and repeating the process for 2-4 times; and then washing the obtained product for 1-5 times by using deionized water until the content of acid radical ions is lower than 0.1wt%, and drying to obtain the dealuminized ZSM-5 molecular sieve.
8. The method of claim 7, wherein: the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and oxalic acid, the dipping treatment temperature is 40-70 ℃, the water washing temperature is 40-70 ℃, and the liquid-solid ratio in the dipping treatment process is (8-12) in ml/g: 1, the liquid-solid ratio in ml/g in the water washing process is (8-12): 1.
9. the method of claim 1, wherein: in the step (2), the dealuminization treatment adopts hydrothermal treatment, and the hydrothermal treatment process comprises the following steps: and carrying out hydrothermal treatment on the ZSM-5 molecular sieve at the temperature of 400-700 ℃ for 0.5-5 h under the steam pressure of 0.05-0.5 MPa to obtain the hydrothermally treated ZSM-5 molecular sieve.
10. The method of claim 1, wherein: and (3) the dealuminization process in the step (2) adopts acid treatment and hydrothermal treatment in sequence.
11. The method of claim 1, wherein: the pH value of the acidic buffer solution in the step (3) is 5.7-6.4, preferably 5.9-6.2, and the specific process is as follows: the treated molecular sieve is placed in a buffer solution for immersion treatment for 0.5-2 h, the liquid-solid volume ratio is (8-12): 1 in ml/g, the treatment temperature is 40-70 ℃, the filtration is carried out after the treatment, and the process is repeated for 2-4 times; and then directly drying or drying after washing to obtain the ZSM-5 molecular sieve treated by the acidic buffer solution.
12. The method of claim 1, wherein: in the step (3), the acidic buffer solution is oxalic acid-ammonium oxalate buffer solution.
13. The method of claim 1, wherein: the supported amino silicone oil in the step (4) adopts an impregnation method, and the impregnation can be equal-volume impregnation or over-volume impregnation, and preferably equal-volume impregnation is carried out.
14. The method of claim 1, wherein: the amino value of the amino silicone oil in the step (4) is 0.6-1.0.
15. The method of claim 1, wherein: in the step (4), the material prepared in the step (3) is soaked in an emulsion containing 0.02-0.10 wt% of amino-containing silicone oil, preferably 0.04-0.06 wt%, in an equal volume, wherein the solvent is deionized water, and the soaking time in an equal volume is 5-10 hours.
16. The method of claim 1, wherein: in the step (4), the drying temperature is 100-150 ℃, and the drying time is 2-4 h; the roasting temperature is 550 ℃; the roasting time is 3-5 h.
17. A ZSM-5 molecular sieve prepared by the process of any of claims 1-16, characterized by: said divisionThe specific surface area of the sub-sieve is 350-500 m2Per g, preferably 400 to 450m2Per g, pore volume of 0.38-0.50 cm3A/g, preferably 0.40 to 0.45cm3The total acid content is 1.6-2.7 mmol/g, preferably 2.0-2.5 mmol/g, the weak acid content is 0.8-1.4 mmol/g, preferably 1.0-1.2 mmol/g, the non-framework aluminum accounts for 6-12%, preferably 8-10%, and the content of the supported silicon oxide is 0.02-0.7 wt%, preferably 0.04-0.06 wt%.
18. The molecular sieve of claim 17, characterized in that: under the reaction pressure of 6.0MPa, the volume ratio of hydrogen to oil of 500:1 and the volume space velocity of 10h -1And under the condition that the reaction temperature is 340 ℃, the ring opening rate of the ZSM molecular sieve to decalin is as follows: 50-70% of n-hexadecane, and the secondary cracking rate of the n-hexadecane is 1-6%.
19. A hydrodewaxing method, a diesel raw material reacts under the action of a hydrodewaxing catalyst, the hydrodewaxing catalyst contains a ZSM-5 molecular sieve prepared by any one of the methods in claims 1-16, and the mass content of polycyclic aromatic hydrocarbons in the raw material oil is higher than 40%, preferably 55-75%.
20. The method of claim 19, wherein: the hydrodewaxing reaction conditions are as follows: the reaction pressure is 5.0-8.0MPa, the volume ratio of hydrogen to oil is 400:1-600:1, the volume space velocity is 8-112 h-1, and the reaction temperature is 280-400 ℃.
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Effective date of registration: 20231214 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |