CN102039171B - Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst - Google Patents
Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst Download PDFInfo
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- CN102039171B CN102039171B CN2009102016573A CN200910201657A CN102039171B CN 102039171 B CN102039171 B CN 102039171B CN 2009102016573 A CN2009102016573 A CN 2009102016573A CN 200910201657 A CN200910201657 A CN 200910201657A CN 102039171 B CN102039171 B CN 102039171B
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- molecular sieve
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- beta zeolite
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 110
- 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 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 81
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000010457 zeolite Substances 0.000 title claims abstract description 81
- 239000011230 binding agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000007493 shaping process Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 45
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- -1 aluminum compound Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 239000011363 dried mixture Substances 0.000 abstract 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000320 mechanical mixture Substances 0.000 abstract 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000465 moulding Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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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Abstract
The invention relates to a preparation method of a non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst. In the invention, the problems that when a hydrothermal synthesis method is adopted to prepare the existing ZSM-5/zeolite beta coexisting molecular sieve, the preparation process is complicated, the cost is higher, the ZSM-5/zeolite beta coexisting molecular sieve catalyst with the binder has lower activity, the non-binder ZSM-5/zeolite beta coexisting molecular sieve has lower strength and the mechanical mixture of ZSM-5 with the binder and zeolite beta has lower activity, are mainly solved. The technical scheme in the invention comprises the following steps: mixing ZSM-5/zeolite beta coexisting molecular sieve, alkaline substance, aluminum compound and silicon oxide, forming, drying, placing the dried mixture in template agent vapor containing at least one of ammonia water, ethylenediamine, triethylamine, n-butylamine, hexanediamine, tetrapropylammonium bromide or tetrapropylammonium hydroxide, and tetraethylammonium hydroxide or tetraethylammonium bromide to perform crystallization treatment at 100-200 DEG C for 10-300 hours and obtain the non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst, wherein the weight contents of ZSM-5/Magadiite coexisting molecular sieve, alkaline substance, aluminum compound and silicon oxide calculated according to the weight of the formed and roasted catalyst are 10-80%, 0.1-10%, 0.5-20%, and 20-80% respectively. The problems can be better solved and the prepared non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst can be used in the naphtha catalytic cracking reaction for preparing propylene.
Description
Technical field
The present invention relates to the preparation method of a kind of adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst.
Background technology
Molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific area and higher thermally-stabilised row, is applied in field of petrochemical industry widely.Because molecular sieve powder self intensity is lower, be prone to disperse to run off, can't directly be applied in use in the industry; Therefore in use need add the binding agent moulding and gain in strength, in the catalyst after the moulding, because binding agent parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, the duct of the molecular sieve of part is blocked, causes the specific area of catalyst lower; Activity is also lower, and again because binding agent is no regular pore passage structure, reaction raw materials and product are in catalyst diffusion difficulty; Carbon deposit has certain influence to life of catalyst easily.Be converted into the active principle molecular sieve to the binding agent in the catalyst and then can overcome above problem, improve activity of such catalysts and diffusion.
The binder free catalyst is exactly the active principle that changes into the binding agent that is added in the molecular sieve catalyst forming process in molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.Be converted into the molecular sieve composition fully owing to binding agent in the binder free catalyst; So just improved the content of molecular sieve in the per volume of catalyst; Make activity of such catalysts higher, treating capacity is bigger, simultaneously owing to no longer include binding agent in the catalyst; Solved binding agent parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that binding agent stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.General Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
General coexisting molecular sieve is to prepare through the synthetic method of hydro-thermal, is Powdered, and no intensity is prone to run off, and can not directly use, and need add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyst reduces, active and diffusion variation.
In the document, the general title of two kinds of molecular sieves of using of the literary style of coexisting molecular sieve is write together at present, and the centre adds one "/" expression, for example, and the coexisting molecular sieve that ZSM-5 and β zeolite are formed, writing " modenite/MCM-22 coexisting molecular sieve ".
At present the binder free catalyst of report has the adhesiveless ZSM-5 molecular sieve, is to make through gas phase conversion at the presoma that preformed catalyst adds ZSM-5.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent ZSM-5 prepare zeolite method is a primary raw material through adopting with diatomite or white carbon; Add the crystal seed directed agents; And with Ludox or sodium metasilicate as the binding agent moulding; Handle the technical scheme that is converted into integrated small-grain ZSM-5 with organic amine mutually with the water vapour gas-solid then.Mainly solve the zeolite powder and in practical application, have the difficult weakness that reclaims, is prone to inactivation and gathering, and the adding binding agent can cause that effective surface area reduces the problem that influences with diffusion restriction in the forming process.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.Through adopting content is the mixture that the former powder of 5～50 weight % binding agent silica and ZSM type molecule forms; In the aqueous solution that contains halogenation organic amine and alkyl diamine or steam; Be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add binding agent in the molecular sieve catalyst forming process and can cause that effective surface area reduces the problem with the diffusion restriction influence.
Composite molecular screen, coexisting molecular sieve or the mixed crystal molecular sieve of existing report all need be synthetic synthetic back of molecular sieve or adding crystal seed directed agents hydro-thermal, and building-up process is very complicated comparatively.The synthetic ZSM-5/ beta zeolite coexisting molecular sieve of report all is to be prepared from through the synthetic method of hydro-thermal at present.Add crystal seed or template in the building-up process, the complicated and pollution again of preparation method.
The method that directly prepares adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst can be optimized preparation process, avoids preparing the process complicated problems, has tangible economic worth and social value.
Summary of the invention
Technical problem to be solved by this invention is that existing ZSM-5/ beta zeolite coexisting molecular sieve prepares and uses hydrothermal synthesis method in the process; The preparation process is complicated; Cost is higher, the relatively poor and lower problem of mechanical impurity activity that contains the ZSM-5 and the β zeolite of binding agent of activity ZSM-5/ beta zeolite coexisting molecular sieve intensity lower, that do not contain binding agent when containing binding agent in the ZSM-5/ beta zeolite coexisting molecular sieve catalyst.A kind of new method for preparing adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst is provided.This method has that the preparation process is simple, and cost is lower, advantages such as environmental protection, and the catalyst of preparation has active higher, simultaneously also advantage of higher of mechanical strength.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: the preparation method of a kind of adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the ZSM-5/ beta zeolite coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0.5～20% aluminium and 10～80% the silica mixed-forming drying; Obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is placed to put into to contain be selected from least a template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, tetraethyl ammonium hydroxide or tetraethylammonium bromide; Carry out the crystallization processing after 20～300 hours at 100-200 ℃, obtain adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst precursor;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%; SiO as the ZSM-5/ beta zeolite coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 20～200; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of period of element Table I A or II A element; The compound of aluminium is at least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium.
In the technique scheme, I A element preferred version is selected from least a in sodium or the potassium, and II A element preferred version is selected from least a in magnesium or the calcium; The salt of weak acid preferred version is selected from least a in carbonate, oxalates or the citrate; In the catalyst weight behind the shaping and roasting, the consumption preferable range of organic amine is 10～100%; The compound amount preferable range of aluminium is 2～15%; The consumption preferable range of molecular sieve is 20～70%; The consumption preferable range of alkaline matter is 0.5～5%; The consumption preferable range of silica is 15～70%; The crystallization temperature preferable range is 120～180 ℃, and the crystallization time preferable range is 20～100 hours.SiO in the prepared ZSM-5/ beta zeolite coexisting molecular sieve
2/ Al
2O
3Preferable range is 20～400; The weight ratio preferable range of ZSM-5 and β zeolite is 0.1～100: 1 in the ZSM-5/ beta zeolite coexisting molecular sieve catalyst, and the binder content preferable range is 0.1～2%, the preformed catalyst intensity preferable range that makes be 60～150 newton/.
It is strip solid cylindrical, that diameter is 0.5～2mm that shape after the catalyst precarsor mixture I extrusion is generally tangent plane, is broken into every grain length degree after the drying and is 5 millimeters short cylindrical shape catalyst bar, is convenient to change brilliant and handles and examination.Catalyst mechanical strength among the present invention is calculated by this shape measure.Catalyst precarsor mixture I also can make cellular as required, clover shape, hollow tubular or shape such as spherical, and its strength criterion is meter in addition.
In the characterization method of binder free catalyst, with the contained thing of XRD test mutually and the content of each thing phase, change the pattern of molecular sieve of situation and the generation of crystalline substance with the scanning electron microscopic observation binding agent.Change brilliant back binder content confirm through the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent confirm.The catalyst silica alumina ratio is confirmed with chemico-analytic method.The strength test method of catalyst is the crushing strength of the catalyst after test roasting on the pressure testing machine; Every of the catalyst of surveying is of a size of 1.5 millimeters of diameters; 5 millimeters of length; Be disposed across on the testing machine, suffered maximum pressure when measuring catalyst breakage is got its mean value after testing 10 catalyst crushing strengths.
The present invention is through adding ZSM-5/ beta zeolite coexisting molecular sieve crystal seed in preformed catalyst; Put into the template steam of specific suitable β zeolite growth, control is suitable for the alkaline environment and the material proportion of ZSM-5 and β zeolite growth simultaneously, makes binding agent under the inducing of crystal seed; Can change into ZSM-5/ beta zeolite coexisting molecular sieve active ingredient; Simultaneously in the control environment of template steam and alkalescence, also can induce the ZSM-5 crystal seed in the binding agent, and can nucleating growth; Therefore binding agent can be transformed into the coexisting molecular sieve active principle through the method for gas phase conversion, obtains binder free type ZSM-5/ β zeolite
The coexisting molecular sieve catalyst; The content of binding agent can reach below 0.5% in the binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst that makes; Even do not contain binding agent; All be ZSM-5/ beta zeolite coexisting molecular sieve in the catalyst, improved the content of coexisting molecular sieve in the per volume of catalyst like this, improved activity of such catalysts.Since change the binder free coexisting molecular sieve thing that obtains behind the crystalline substance mutually between staggered growth, in conjunction with tightr, so the intensity of catalyst is also higher, can reach 180 newton/more than.The catalyst that makes can be used in the reaction of naphtha catalytic pyrolysis preparing propylene, and the diene weight yield of ethylene, propylene can reach more than 54%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Fig. 2 is the ESEM picture of the adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Get SiO
2/ Al
2O
3Mol ratio is 60 ZSM-5/ beta zeolite coexisting molecular sieve molecular sieve 60 grams, and the adding weight percentage is 40% Ludox 40 grams and aluminum sulfate 16 grams, after the mixing and stirring; 10 milliliters of sodium carbonate liquors that add 0.5 mol again, mixing and stirring, the moulding of agent bar then; Preformed catalyst is 80 ℃ of oven dry 3 hours, put into then the inner bag bottom moisture with the hexamethylene diamine mass ratio be 1: 1 200 milliliters of mixed solution 40 gram autoclave, catalyst does not contact with liquid water; Put into baking oven after the autoclave sealing, 165 ℃ of crystallization were taken out after 60 hours, washed then 2 times; Put into 120 ℃ in baking oven oven dry 3 hours, putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours; Make adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst, wherein the weight percentage of ZSM-5 molecular sieve is 43.5%, and the β zeolite content is 56.0%; The XRD figure spectrum of the catalyst that makes is as shown in Figure 1, and it is shown as the thing phase of ZSM-5/ β zeolite.The ESEM picture of the catalyst that makes is as shown in Figure 2, and it is shown as the mixture of ball-type ZSM-5 crystal grain and β zeolite grain, and the binder content of unformed state is 0.5%.
[embodiment 2～6]
According to the method for embodiment 1, get SiO respectively
2/ Al
2O
3Mol ratio is that 20,60,100,160 and 200 ZSM-5/ beta zeolite coexisting molecular sieve is as crystal seed; Other condition is constant, and it is as shown in table 1 that raw material is formed proportioning, and the adhesiveless ZSM-5 that makes/beta zeolite coexisting molecular sieve catalyst is as shown in table 2.
[embodiment 7～13]
Method according to embodiment 1; Other condition is constant, in forming process, adds soluble starch, sesbania powder or methylcellulose, and it is as shown in table 1 that raw material is formed proportioning; Mixing and stirring; Extruded moulding is processed adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst by the method for embodiment 1 again, and the result is as shown in table 2.
[embodiment 14]
Method according to embodiment 1 makes the binder free catalyst; Use concentration is 5% ammonium nitrate solution; It in the solid-to-liquid ratio of catalyst and ammonium nitrate solution 1: 10 ratio; 90 ℃ of exchanges three times, 550 ℃ of roastings made the adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index is seen table 3), the examination activity of such catalysts, using diameter is 12 millimeters fixed bed reactors normal pressure examination down, range of reaction temperature is 650 ℃, reaction pressure is 0.02MPa, mass space velocity is 1 hour
-1, water/feedstock oil mass ratio is 1: 1, the reaction half an hour after, products distribution is seen table 4, feed stock conversion is 96%, the ethene mass yield is 28.0%, the propylene mass yield is 27.0%, diene quality total recovery is 55.0%.
Table 2
| Embodiment | Gained adhesiveless ZSM-5/beta zeolite coexisting molecular sieve SiO 2/Al 2O 3 | ZSM-5 content (weight %) in gained adhesiveless ZSM-5/beta zeolite coexisting molecular sieve | β zeolite content (weight %) in gained adhesiveless ZSM-5/beta zeolite coexisting molecular sieve | Binder content in the gained catalyst (weight %) | Gained binder free catalyst strength (newton /) |
| |
30 | 73.0 | 26.0 | 1 | 120 |
| Embodiment 3 | 82 | 35.8 | 63.6 | 0.6 | 170 |
| Embodiment 4 | 120 | 45.0 | 53.8 | 1.2 | 150 |
| Embodiment 5 | 200 | 38.5 | 59.4 | 2.1 | 150 |
| Embodiment 6 | 340 | 1.5 | 98.5 | 0 | 190 |
| Embodiment 7 | 80 | 10.0 | 88.5 | 1.5 | 175 |
| Embodiment 8 | 400 | 65.4 | 33.2 | 1.4 | 175 |
| Embodiment 9 | 350 | 71.4 | 23.6 | 5.0 | 80 |
| |
180 | 10.2 | 88.2 | 1.6 | 160 |
| Embodiment 11 | 30 | 13.9 | 86.0 | 0.1 | 200 |
| Embodiment 12 | 60 | 55.0 | 40.5 | 4.5 | 110 |
| Embodiment 13 | 240 | 10.7 | 85.4 | 3.9 | 90 |
[embodiment 15]
Get the binder free type ZSM-5/ β zeolite that obtains among the embodiment 1, process hydrogen type catalyst, get 100 grams by the method for embodiment 14; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.5 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst of phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
Table 3 light oil raw material index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.2 |
| Cycloalkane % (weight %) | 28.4 |
| Alkene % (weight %) | 0.2 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
[embodiment 16]
Get binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst 100 grams of the phosphorus modification that obtains among the embodiment 15; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.2 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst of lanthanum and phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; Then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5/ β zeolite mixed crystal molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5 molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; Then ZSM-5 molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve; Then β zeolite direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 5]
The silica alumina ratio that Oil of Shanghai Petrochemical Company research institute produces is 40 ZSM-5 molecular sieve; By processing hydrogen type molecular sieve by the method for embodiment 14; And then, obtain containing the ZSM-5 molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 6]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the beta zeolite coexisting molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 7]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5, and silica alumina ratio is 40 β zeolite, is mixed into mechanical impurity at 1: 1 according to weight ratio; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5 of binding agent and the catalyst of β zeolite mechanical impurity according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
Table 4
| Products distribution | Product weight yield (%) |
| Methane | 4.5 |
| Ethane | 6.5 |
| Ethene | 28.0 |
| Propane | 6.1 |
| Propylene | 27.5 |
| Butane | 8.2 |
| Butylene | 7.4 |
| Carbon five above cuts | 8.3 |
| Other | 3.5 |
Table 5
| Embodiment | Catalyst strength (newton /) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) | React 0.5 hour conversion ratio (%) |
| Embodiment 15 | 143 | 28.5 | 27 | 55.5 | 97.5 |
| Embodiment 16 | 138 | 28 | 24 | 52 | 96 |
| Comparative example 1 | 30 | 23 | 22 | 45 | 90 |
| Comparative example 2 | 80 | 22 | 21 | 43 | 86 |
| Comparative example 3 | 32 | 22 | 20 | 42 | 84 |
| Comparative example 4 | 31 | 20 | 21 | 41 | 82 |
| Comparative example 5 | 75 | 22 | 21 | 43 | 80 |
| Comparative example 6 | 65 | 24 | 20 | 44 | 82 |
| Comparative example 7 | 68 | 25 | 22 | 47 | 87 |
Claims (7)
1. the preparation method of adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the ZSM-5/ beta zeolite coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0.5～20% aluminium and 10～80% the silica mixed-forming drying; Obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is put into to contain be selected from least a template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, tetraethyl ammonium hydroxide or tetraethylammonium bromide; Carry out the crystallization processing after 20～300 hours at 100-200 ℃, obtain adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst precursor;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%; SiO as the ZSM-5/ beta zeolite coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 20～200; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of periodic table of elements IA family or IIA family element; The compound of aluminium is at least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium; Wherein the Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
2. the preparation method of adhesiveless ZSM-5 according to claim 1/beta zeolite coexisting molecular sieve catalyst is characterized in that IA family element is selected from least a in sodium or the potassium, and IIA family element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in carbonate, oxalates or the citrate.
3. the preparation method of adhesiveless ZSM-5 according to claim 1/beta zeolite coexisting molecular sieve catalyst, in the catalyst weight behind the shaping and roasting, the consumption of ZSM-5/ beta zeolite coexisting molecular sieve is 20～70%; The consumption of alkaline matter is 0.5～5%; The compound amount of aluminium is 2～15%; The consumption of silica is 15～70%; Template agent is 10～100%.
4. the preparation method of adhesiveless ZSM-5 according to claim 1/beta zeolite coexisting molecular sieve catalyst is characterized in that crystallization temperature is 120～180 ℃, and crystallization time is 20～100 hours.
5. the preparation method of adhesiveless ZSM-5 according to claim 1/beta zeolite coexisting molecular sieve catalyst; It is characterized in that in the catalyst weight behind the shaping and roasting, also contain 0.1～2% the expanding agent at least a in sesbania powder, methylcellulose or the soluble starch that is selected among the preformed catalyst precursor mixture I.
6. the preparation method of adhesiveless ZSM-5 according to claim 1/beta zeolite coexisting molecular sieve catalyst is characterized in that the adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst that makes contains SiO
2/ Al
2O
3Mol ratio is 20～400 ZSM-5/ β zeolite, weight of binder content 0～5%; The weight ratio of ZSM-5 and β zeolite is 0.15～100: 1 in the ZSM-5/ beta zeolite coexisting molecular sieve, is of a size of 1.5 millimeters of diameters with every of surveyed catalyst, 5 millimeters meters of length, the mechanical strength of preformed catalyst be 50～200 newton/.
7. the preparation method of adhesiveless ZSM-5 according to claim 6/beta zeolite coexisting molecular sieve catalyst; It is characterized in that in the catalyst weight behind the shaping and roasting weight of binder content is 0.1～2% in the adhesiveless ZSM-5 that makes/beta zeolite coexisting molecular sieve catalyst.
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