CN101468318B - Modified rare-earth-containing molecular sieve catalyst as well as preparation method and use thereof - Google Patents
Modified rare-earth-containing molecular sieve catalyst as well as preparation method and use thereof Download PDFInfo
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- CN101468318B CN101468318B CN2007103042896A CN200710304289A CN101468318B CN 101468318 B CN101468318 B CN 101468318B CN 2007103042896 A CN2007103042896 A CN 2007103042896A CN 200710304289 A CN200710304289 A CN 200710304289A CN 101468318 B CN101468318 B CN 101468318B
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- 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 104
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 23
- 238000012986 modification Methods 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 10
- 239000011654 magnesium acetate Substances 0.000 claims description 10
- 235000011285 magnesium acetate Nutrition 0.000 claims description 10
- 229940069446 magnesium acetate Drugs 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000012702 metal oxide precursor Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- KXEOSTAFIDYVEF-UHFFFAOYSA-N [Si](O)(O)(O)O.[F] Chemical compound [Si](O)(O)(O)O.[F] KXEOSTAFIDYVEF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- -1 rare-earth salts Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229940001007 aluminium phosphate Drugs 0.000 claims description 2
- 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 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011265 semifinished product Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a rare-earth-containing ZSM-5 molecular sieve catalyst modified with metallic oxide, which ensures high propylene selectivity, high methanol conversion rate and long life span of the catalyst in reaction which takes methanol and/or dimethyl ether as raw material to prepare low-carbon olefin. The catalyst consists of metallic oxide, binder and modified molecular sieves, wherein the metallic oxide accounts for 1 to 10 percent; the binder accounts for 5 to 30 percent; the modified molecular sieves account for 60 to 90 percent; and the modified molecular sieves contain rare earth oxide Ce2O3 and La2O3. The catalyst is used in the field of petrochemical industry.
Description
Technical field
The present invention relates to a kind of catalyst, be specifically related to Catalysts and its preparation method and application that the low-carbon alkene of propylene is rich in a kind of preparation.
Background technology
Low-carbon alkene such as ethene, propylene is most important basic Organic Chemicals, and wherein propylene is one of product that demand growth is the fastest in the world at present.Traditional is the production method of raw material with crude oil, reclaims propylene as naphtha pyrolysis and refinery gas, has been difficult to satisfy growing demand.Soar as the crude oil price of producing low-carbon alkene raw materials such as ethene, propylene, and face the crisis of scarcity of resources.Therefore, exploitation is with other raw material, and for example coal, natural gas replace the technology of crude oil production ethene, propylene to have great development prospect.This technology utilization has the mature industry technology now, at first coal and natural gas via synthesis gas (gaseous mixture of carbon monoxide and hydrogen) are converted into methyl alcohol and dimethyl ether, utilize molecular sieve catalyst that methyl alcohol and dimethyl ether further are converted into low-carbon alkenes such as ethene, propylene.
Methyl alcohol and dimethyl ether conversion are that molecular sieve catalyst and the production technology that low-carbon alkene uses is broadly divided into two classes.One class be U.S. Pat 4440871 disclosed be the catalyst of main active component with aperture aluminium silicophosphate molecular sieve SAPO-34.Because methyl alcohol very easily forms coking in the SAPO-34 molecular sieve pore passage in course of reaction, must adopt the fluid bed production technology, by high-temp combustion continuously, remove the carbon deposit that produces in the course of reaction, regenerated catalyst, production cost is higher.
Second class is to adopt the ZSM-5 molecular sieve catalyst with MFI structure.Such molecular sieve catalyst is poorer than selectivity of light olefin such as the ethene of SAPO-34 molecular sieve, propylene, but it is relatively slow to have coking speed, the advantage that the regeneration period is long.For improving selectivity and the stability that the ZSM-5 molecular sieve catalyst changes into low-carbon alkenes such as ethene, propylene, need carry out modification to the ZSM-5 molecular sieve.
U.S. Pat 4480145 is by carrying out cycle life and the methanol conversion that high-temperature water heat treatment improves ZSM-5 to the ZSM-5 molecular sieve under 180～820 ℃.
U.S. Pat 4247731 and US4296266 on the X molecular sieve with Mg or other metal ion for example Mn carry out modification, improve selectivity of ethylene from preparing light olefin by carbinol.
U.S. Pat 4665268 obtains the Mg-Mn/ZSM-12 catalyst by exchanging the ZSM-12 molecular sieve separately or jointly with Mg, Mn, and the preparation that is used to be rich in the low-carbon alkene of propylene has better selectivity, C
2 =Be 3.8%, C
3 =Be 59.5%.But methanol conversion is lower, is 91.9%, C
2 =～C
4 =The yield of alkene is the highest to have only 80.2%.This will make increases a large amount of unreacted methanol circulations and produces and equipment cost, and a large amount of C are arranged
5Above accessory substance.
Chinese patent CN1039392C provides a kind of phosphorous, the rare earth element of preparing low carbon olefinic hydrocarbon with methanol and the ZSM-5 molecular sieve catalyst of pore structure conditioning agent to have higher C
2 =～C
4 =Selectivity is greater than 85%.But catalyst is very fast to need high temperature regeneration that carbon deposit is removed because of a large amount of carbon deposit rapid deactivations in surface, recovers activity of such catalysts.The one way catalyst life has only 24 hours, and regeneration is frequent.For making methanol conversion reach 100%, reaction temperature is controlled at 500～550 ℃.
Summary of the invention
The technical problem to be solved in the present invention is: for overcoming the deficiency that the selectivity of propylene is lower in the prior art, conversion of methanol is not high and catalyst life is short, a kind of rare-earth-containing molecular sieve catalyst of modification is provided, make that at methyl alcohol and/or dimethyl ether be in the reaction of feedstock production low-carbon alkene, propylene selectivity and methanol conversion height, catalyst life are long.And provide this Preparation of catalysts methods and applications.
Product technology scheme of the present invention is:
A kind of rare-earth-containing molecular sieve catalyst of modification is used for from methyl alcohol and/or dimethyl ether production low-carbon alkene, and low-carbon alkene refers to C
2～C
4Alkene.
This catalyst is made up of metal oxide, binding agent, modified molecular screen; In the gross mass of described catalyst, described metal oxide accounts for: 1%～10%, and described binding agent accounts for: 5%～30%, described modified molecular screen accounts for: 60%～90%;
Described metal oxide is at least a in following: MnO, MnO
2, Mn
2O
3, Mn
3O
4, MgO;
Described binding agent is at least a in following: SiO
2, Al
2O
3
Described modified molecular screen is: have the ZSM-5 structure; In described modified molecular screen in molar ratio,
SiO
2∶Al
2O
3＝80～120∶1；
In molecular sieve, contain SiO
2, Al
2O
3, with the SiO in the binding agent
2, Al
2O
3Irrelevant.
Described modified molecular screen contains rare earth oxide Ce
2O
3And La
2O
3, press mass ratio,
Ce
2O
3∶La
2O
3＝1～3∶1；
Account for 0.5%～15% at rare earth oxide described in the described modified molecular screen gross mass.
Further optimize, in the gross mass of described catalyst, described binding agent accounts for: 5%～15%.
In the gross mass of described catalyst, described modified molecular screen accounts for: 70%～90%.
Account for 1%～5% at rare earth oxide described in the described modified molecular screen gross mass.
Molecular sieve characterizes out the aperture of molecular sieve to the adsorbance of n-hexane and cyclohexane, and preferred version is: described modified molecular screen is 100～110 a milligrams/gram for the adsorbance of n-hexane, and promptly every gram molecule sieve can adsorb 100～110 milligrams of n-hexanes; Described modified molecular screen is 15～20 a milligrams/gram for the adsorbance of cyclohexane.
The crystal grain diameter of described modified molecular screen is 0.5～10 micron.
Preparation method's scheme of the present invention is may further comprise the steps:
The first step, the system molecular sieve
The 1.1st step was a crystal seed with the ZSM-5 molecular sieve that contains rare earth, and described crystal seed contains rare earth oxide Ce
2O
3And La
2O
3, press mass ratio, Ce
2O
3: La
2O
3=1～3: 1;
In the gross mass of described crystal seed, above-mentioned rare earth oxide accounts for 5%～25%;
Crystal seed can be made by oneself, also can buy existing goods on market.
Described crystal seed and silicon source, aluminium source are mixed;
Described silicon source is at least a in following: waterglass, sodium silicate aqueous solution;
Described aluminium source is at least a in following: aluminum sulfate aqueous solution, the alchlor aqueous solution, aluminium phosphate aqueous solution;
The 1.2nd step, with said mixture with following inorganic acid for adjusting pH value to 10～12, in the mixture that obtains in molar ratio:
SiO
2∶Al
2O
3＝50～120∶1
Na
2O∶Al
2O
3＝2～15∶1
H
2O∶SiO
2＝20～100∶1
Described inorganic acid is at least a in following: phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid;
In the 1.3rd step, be heated to 150 ℃～200 ℃, crystallization 20～40 hours with said mixture is airtight; Be conventional steps.
In the 1.4th step, cooling is filtered, washing, drying; Obtain containing the sodium type ZSM-5 molecular sieve of rare earth; Be conventional steps.
In the 1.5th step, contain the sodium type ZSM-5 molecular sieve of rare earth and contain NH above-mentioned
4 +The aqueous solution of ion carries out ion-exchange, makes Na in the molecular sieve
2O content is reduced to and is not more than 0.1%; Dry then; Be conventional steps.
The 1.6th step, will go up step product and fluorine silicic acid aqueous solution and carry out dealumination reaction, washing, drying are conventional steps then.Sial ratio in the products therefrom, silicon is with SiO
2Meter, aluminium is with Al
2O
3Meter is in molar ratio:
SiO
2∶Al
2O
3＝80～120∶1
Obtain containing the ammonium type ZSM-5 molecular sieve of rare earth;
Second step, moulding
The 2.1st step added binding agent in first step gained contains the ammonium type ZSM-5 molecular sieve of rare earth, described binding agent is at least a in following: SiO
2, Al
2O
3
Press mass ratio, molecular sieve: binding agent=1: 0.05～0.35
In the 2.2nd step, moulding, drying, roasting obtain containing the Hydrogen ZSM-5 molecular sieve of rare earth; Be conventional steps.
The 3rd step, dipping
The 3.1st step is with the above-mentioned Hydrogen ZSM-5 molecular sieve that contains rare earth, with the aqueous solution of metal oxide precursor; Described metal oxide precursor is at least a in following: water-soluble Mg salt, water-soluble Mn salt; Press mass ratio, wherein metal oxide precursor is in corresponding metal oxide MnO or MgO,
Molecular sieve: metal oxide: water=1: 0.01～1: 0.1～10
Make metal oxide impregnated to molecular sieve;
In the 3.2nd step, drying is conventional steps.Obtain the Hydrogen ZSM-5 molecular sieve that contains rare earth of modification;
The 4th step, high-temperature water heat treatment
The 4.1st the step, with steam-laden air be passed into the 3rd the step gained molecular sieve, under 450 ℃～650 ℃ conditions, the processing time is no less than 2 hours, water consumption is not less than 5 times of described molecular sieve quality; By steam the water-solubility impurity in the molecular sieve is washed off, so that catalyst is stable.
The 4.2nd step, roasting more than 3 hours in air, 450 ℃～650 ℃ of sintering temperatures obtain the rare-earth-containing molecular sieve catalyst of modification as claimed in claim 1.
Crystal seed can adopt following method preparation:
In the 1.1st step, the described ZSM-5 molecular sieve crystal seed that contains rare earth, by comprising the steps preparation:
(1) get commodity ZSM-5 molecular sieve, wherein in molar ratio,
SiO
2∶Al
2O
3＝50～120∶1
(2) preparation contains CeCl
3And LaCl
3The rare-earth salts acid solution, wherein press mass ratio,
CeCl
3∶LaCl
3＝1～3∶1
Under 80 ℃～120 ℃ temperature, above-mentioned commodity ZSM-5 molecular sieve was carried out ion-exchange 0.5～1.5 hour with above-mentioned rare-earth salts acid solution;
(3) to the molecular sieve filtration after the ion-exchange, under 400 ℃～600 ℃ temperature, roasting 2～4 hours;
Repetition (2), (3) step, reach 5%～25% of molecular sieve gross mass until rare earth oxide content; Obtain the described ZSM-5 molecular sieve crystal seed that contains rare earth.
Further optimize, in the 1.1st step, described aluminium source is: aluminum phosphate;
In the 1.2nd step, described inorganic acid is: phosphoric acid.
In the 3.1st step, described metal oxide precursor is at least a in following: magnesium acetate, manganese acetate, manganese nitrate, magnesium hydroxide, magnesium dichloride, manganous chloride.
In the 3.1st step, described metal oxide precursor is at least a in following: magnesium acetate, manganese acetate.
The rare-earth-containing molecular sieve catalyst of above-mentioned modification is used for from the reaction of methyl alcohol and/or dimethyl ether production low-carbon alkene.
Low-carbon alkene refers to C
2～C
4Alkene.Use the rare-earth-containing molecular sieve catalyst of modification of the present invention, the propylene content of generation is greater than 45%, C
3 =: C
2 =＞4.5, catalyst of the present invention can be applied in the various reactors, for example, and fixed bed reactors, fluidized-bed reactor, moving-burden bed reactor etc.
The present invention is the high-silica zeolite of crystal seed preparation with the ZSM-5 that contains rare earth, the adsorbance of its n-hexane is close with common molecular sieve, but the adsorbance of cyclohexane is starkly lower than common ZSM-5 molecular sieve, and the absorption mass ratio of the adsorbance of n-hexane and cyclohexane is 5～6.And the absorption mass ratio of the adsorbance of common REZSM-5 molecular sieve n-hexane and cyclohexane is generally 3～4.Therefore, the present invention is that the high-silica zeolite that crystal seed prepares has the five circular ring structure ducts narrower than common molecular sieve with the ZSM-5 that contains rare earth, helps improving selectivity of light olefin.
The invention has the beneficial effects as follows:
Use catalyst of the present invention, produce in the product of low-carbon alkene reaction at methyl alcohol and/or dimethyl ether, the selectivity of propylene is greater than 45%; Conversion of methanol is near 100%; Catalyst junction carbon amount reduces, and the one way life cycle of catalyst was greater than 280 hours; Catalyst can use by repeated regeneration.The another one advantage of catalyst of the present invention is that reaction temperature is relatively low, can transform fully at 450 ℃ of methyl alcohol.
The specific embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1
Take by weighing 100 commercially available gram ZSM-5 molecular sieve (SiO
2: Al
2O
3=80), join 2000 gram RECl
3In the aqueous solution, RE represents Rare-Earth Ce and La, RECl in this aqueous solution
3Mass content is 2%, CeCl
3: LaCl
3=2: 1.Stir then, carry out ion-exchange 50 minutes under 95 ℃, filter, 550 ℃ of following roastings 2 hours repeat above-mentioned steps once, make RE
2O
3The quality percentage composition is 21% RE-ZSM-5 crystal seed.
Take by weighing the above-mentioned RE-ZSM-5 crystal seed of 30 grams, add in the 1800 gram water glass solutions; Na in the water glass solution
2O mass content 3.6%, SiO
2Mass content 12%.Stir, add 300 grams and contain 1.0%Al
2O
3Aluminum phosphate colloidal solution, be that 8% phosphoric acid solution is regulated pH value to 10.5 with concentration.This system was 180 ℃ of following crystallization 20 hours, and cooling is filtered, and washed to neutrality 120 ℃ of dryings 3 hours with water.
With above-mentioned RE-NaZSM-5 molecular sieve and ammonium sulfate solution according to mass ratio condition composed as follows,
Molecular sieve: (NH
4)
2SO
4: H
2O=1: 1: 20
Carry out ion-exchange 1 hour under 85 ℃, filter, drying repeats ion-exchange and filtration, washing.
Add fluorine silicic acid aqueous solution according to following mass ratio,
Ammonium type molecular sieve: 2.5% fluorine silicic acid aqueous solution=1: 10
Dealumination reaction is 2 hours under 80 ℃ of stirrings, washing, 120 ℃ of dryings 3 hours.
Through chemical method and X-ray fluorescence analysis, prepared molecular sieve contains 2.2%RE
2O
3, be SiO in molar ratio
2: Al
2O
3=100.
X-ray diffraction spectra shows that this molecular sieve is the ZSM-5 molecular sieve with five-membered ring crystal structure.The crystal grain diameter of crystal is 1～4.5 micron.The adsorbance of n-hexane is 103 a milligrams/gram, and the adsorbance of cyclohexane is 18 a milligrams/gram.The adsorbance of n-hexane is 5.7 in the adsorbance ratio of cyclohexane.
Embodiment 2
Get the 2.2%RE that contains of 100 gram embodiment, 1 preparation
2O
3The RE-ZSM-5 molecular sieve, in molar ratio, SiO
2: Al
2O
3=100,
Add 15 gram alumina dry glues, mix, be extruded into the strip of diameter 3mm.120 ℃ of oven dry 3 hours, 450 ℃ of roastings 4 hours.Be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product.
Embodiment 3
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, with 7 gram mass percentage compositions 10% magnesium acetate solution, flooded 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, with 100ml water 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepares finished catalyst A.By analysis, MgO quality percentage composition is 1.9% in the catalyst.
Embodiment 4
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, with 7 gram mass percentage compositions 20% magnesium acetate solution, flooded 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, repeating with 7 gram mass percentage compositions was 20% magnesium acetate solution again, at 60 ℃ of dippings 3 hours down, 120 ℃ of dryings 3 hours, 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepared finished catalyst B with 100ml water.By analysis, MgO quality percentage composition is 7.5% in the catalyst.
Embodiment 5
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, with 7 gram mass percentage compositions 20% manganese acetate solution, flooded 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, with 100ml water 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepares finished catalyst C.By analysis, MnO quality percentage composition is 5.2% in the catalyst.
Embodiment 6
Get the RE-HZSM-5 molecular sieve catalyst semi-finished product of 10 gram embodiment, 2 preparations, with 7.5 gram mass percentage compositions is that 25% magnesium acetate and 7.5 gram mass percentage compositions are 6.5% manganese acetate solution, flooded 3 hours down at 50 ℃, 120 ℃ of dryings 3 hours, with 100ml water 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepares finished catalyst D.By analysis, MgO quality percentage composition is 5.3% in the catalyst, and MnO quality percentage composition is 1.9%.
Embodiment 7
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, with 7 gram mass percentage compositions is that 10% magnesium acetate and 7 gram mass percentage compositions are 7% manganese acetate solution, flooded 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, with 100ml water 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepares finished catalyst E.By analysis, MgO quality percentage composition is 1.9% in the catalyst, and MnO quality percentage composition is 1.9%.
Embodiment 8
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, with 7.5 gram mass percentage compositions is that 10% magnesium acetate and 7.5 gram mass percentage compositions are 20% manganese acetate solution, flooded 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, with 100ml water 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepares finished catalyst F.By analysis, MgO quality percentage composition is 1.9% in the catalyst, and MnO quality percentage composition is 6.0%.
Comparative Examples 1
Get 10 gram embodiment 2 and be prepared into RE-HZSM-5 molecular sieve catalyst semi-finished product, 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepared comparative catalyst G with 100ml water.
Embodiment 9
Get catalyst A, B, C, D, E, each 5 gram of F, G of embodiment 3～8 and Comparative Examples 1 preparation respectively, be ground into particle diameter 0.50mm～0.85mm respectively, load 1.5 respectively and restrain in the stainless steel fixed bed reactors of internal diameter 6mm, catalyst is estimated.450 ℃ of reaction temperatures, reaction pressure 0.05MPa, in methyl alcohol, mass space velocity is 2.0h
-1, raw material is a methanol aqueous solution, presses mass ratio,
Methyl alcohol: water=3: 7,
Liquid product adopts the mixture of ice and water cooling, collects post analysis, and gas-phase product directly enters gas chromatograph and analyzes its composition and content.
Evaluation result sees Table 1.The catalyst that utilizes the present invention to prepare can be the light olefin that is rich in propylene with methanol conversion.C
2 =～C
4 =Olefin yields greater than 85%, C
3 =: C
2 =Be up to 4.6, methanol conversion is 100%.
The C of comparative catalyst G
2 =～C
4 =Olefin yields be 78.5%, C
3 =: C
2 =Be 2.6, illustrate that metal oxide is to the further effect that improves the selectivity of light olefin of rare-earth-containing molecular sieve catalyst.
Table 1: catalyst performance evaluation result
Embodiment 10
Catalyst D with embodiment 6 preparations carries out life test, and reaction condition is with embodiment 9, and filling 15 restrains in the stainless steel fixed bed reactors of internal diameter 10mm.Operation is after 280 hours continuously for catalyst, and methanol conversion reduces to 98% from 100%.Stop the charging of methanol aqueous solution, logical nitrogen replacement.Catalyst is under 500 ℃, at air speed 1000h
-1Under the condition, feed oxygen content and be 10% nitrogen 24 hours, remove the coking in the catalyst.Repeat the methanol conversion reaction then, after catalyst moved 270 hours continuously, methanol conversion reduced to 98% from 100%.In the cycle of operation, C
2 =～C
4 =Olefin yields greater than 84%, C
3 =: C
2 =Greater than 4.0, methanol conversion is 100%.This experiment shows that methanol conversion catalyst that the present invention prepares can repeat regeneration and use, and one way running time was greater than 280 hours, and propylene content can reach more than 45% in the low-carbon alkene.
Comparative Examples 2
Get 100 commercially available gram ZSM-5 molecular sieve, SiO in molar ratio of 100 grams
2: Al
2O
3=80, containing the rare earth oxide mass content with ion-exchange process preparation is 2.1% RE-ZSM-5, and the adsorbance of its n-hexane is 102.5 a milligrams/gram, and the adsorbance of cyclohexane is 32.3 a milligrams/gram.Add 15 gram alumina dry glues, mix, be extruded into the strip of diameter 3mm.120 ℃ of oven dry 3 hours, 450 ℃ of roastings 4 hours.Getting wherein 10 gram RE-ZSM-5, is 10% magnesium acetate solution with 7 gram mass content, floods 3 hours down at 60 ℃, 120 ℃ of dryings 3 hours, 500 ℃ of following steam treatment 3 hours, roasting 6 hours in 550 ℃ of air again prepared comparative catalyst H with 100ml water.By analysis, the MgO mass content is 1.85% among the comparative catalyst H.Method according to embodiment 9 is estimated.C
2 =Yield is 19.7%, C
3 =Yield is 32.3%, C
4 =Yield is 17.4%, C
2 =～C
4 =Yield be 69.4%, C
3 =: C
2 =Have only 1.60.
The comparative catalyst H explanation of comparing with catalyst A utilizes the rare-earth-containing molecular sieve catalyst of the modification that the present invention prepares than conventional rare earth ZSM-5 higher selectivity of light olefin to be arranged.
Claims (9)
1. the rare-earth-containing molecular sieve catalyst of a modification is used for from methyl alcohol and/or dimethyl ether production C
2～C
4Alkene, it is characterized in that:
This catalyst is made up of metal oxide, binding agent, modified molecular screen; In the gross mass of described catalyst, described metal oxide accounts for: 1%～10%, and described binding agent accounts for: 5%～30%, described modified molecular screen accounts for: 60%～90%;
Described metal oxide is at least a in following: MnO, MnO
2, Mn
2O
3, Mn
3O
4, MgO;
Described binding agent is at least a in following: SiO
2, Al
2O
3
Described modified molecular screen is: have the ZSM-5 structure; In described modified molecular screen in molar ratio,
SiO
2∶Al
2O
3＝80～120∶1；
Described modified molecular screen contains rare earth oxide Ce
2O
3And La
2O
3, press mass ratio,
Ce
2O
3∶La
2O
3＝1～3∶1；
Account for 0.5%～15% at rare earth oxide described in the described modified molecular screen gross mass.
2. the rare-earth-containing molecular sieve catalyst of modification according to claim 1 is characterized in that:
Account for 1%～5% at rare earth oxide described in the described modified molecular screen gross mass.
3. the rare-earth-containing molecular sieve catalyst of modification according to claim 1 is characterized in that:
Described modified molecular screen is 100～110 a milligrams/gram for the adsorbance of n-hexane, and described modified molecular screen is 15～20 a milligrams/gram for the adsorbance of cyclohexane.
4. according to the rare-earth-containing molecular sieve catalyst of the described modification of one of claim 1 to 3, it is characterized in that: the crystal grain diameter of described modified molecular screen is 0.5～10 micron.
5. the preparation method of the rare-earth-containing molecular sieve catalyst of a modification is characterized in that may further comprise the steps:
The first step, the system molecular sieve
The 1.1st step was a crystal seed with the ZSM-5 molecular sieve that contains rare earth, and described crystal seed contains rare earth oxide Ce
2O
3And La
2O
3, press mass ratio, Ce
2O
3: La
2O
3=1～3: 1;
In the gross mass of described crystal seed, above-mentioned rare earth oxide accounts for 5%～25%;
Described crystal seed and silicon source, aluminium source are mixed;
Described silicon source is: sodium silicate aqueous solution;
Described aluminium source is at least a in following: aluminum sulfate aqueous solution, the alchlor aqueous solution, aluminium phosphate aqueous solution;
The 1.2nd step, with said mixture with following inorganic acid for adjusting pH value to 10～12, in the mixture that obtains in molar ratio:
SiO
2∶Al
2O
3＝50～120∶1
Na
2O∶Al
2O
3＝2～15∶1
H
2O∶SiO
2＝20～100∶1
Described inorganic acid is at least a in following: phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid;
In the 1.3rd step, be heated to 150 ℃～200 ℃, crystallization 20～40 hours with said mixture is airtight;
In the 1.4th step, cooling is filtered, washing, drying; Obtain containing the sodium type ZSM-5 molecular sieve of rare earth;
In the 1.5th step, contain the sodium type ZSM-5 molecular sieve of rare earth and contain NH above-mentioned
4 +The aqueous solution of ion carries out ion-exchange, makes Na in the molecular sieve
2O content is reduced to and is not more than 0.1%; Dry then;
The 1.6th step, will go up step product and fluorine silicic acid aqueous solution and carry out dealumination reaction, wash then, drying, the sial ratio in the products therefrom, silicon is with SiO
2Meter, aluminium is with Al
2O
3Meter is in molar ratio:
SiO
2∶Al
2O
3＝80～120∶1
Obtain containing the ammonium type ZSM-5 molecular sieve of rare earth;
Second step, moulding
The 2.1st step added binding agent in first step gained contains the ammonium type ZSM-5 molecular sieve of rare earth, described binding agent is at least a in following: SiO
2, Al
2O
3
Press mass ratio, molecular sieve: binding agent=1: 0.05～0.35
In the 2.2nd step, moulding, drying, roasting obtain containing the Hydrogen ZSM-5 molecular sieve of rare earth;
The 3rd step, dipping
The 3.1st step is with the above-mentioned Hydrogen ZSM-5 molecular sieve that contains rare earth, with the aqueous solution of metal oxide precursor; Described metal oxide precursor is at least a in following: water-soluble Mg salt, water-soluble Mn salt; Press mass ratio, wherein metal oxide precursor is in corresponding metal oxide MnO or MgO,
Molecular sieve: metal oxide: water=1: 0.01～1: 0.1～10
Make metal oxide impregnated to molecular sieve;
In the 3.2nd step, drying obtains the Hydrogen ZSM-5 molecular sieve that contains rare earth of modification;
The 4th step, high-temperature water heat treatment
The 4.1st the step, with steam-laden air be passed into the 3rd the step gained molecular sieve, under 450 ℃～650 ℃ conditions, the processing time is no less than 2 hours, water consumption is not less than 5 times of described molecular sieve quality;
The 4.2nd step, roasting more than 3 hours in air, 450 ℃～650 ℃ of sintering temperatures obtain the rare-earth-containing molecular sieve catalyst of modification as claimed in claim 1.
6. the preparation method of the rare-earth-containing molecular sieve catalyst of modification according to claim 5 is characterized in that:
In the 1.1st step, the described ZSM-5 molecular sieve crystal seed that contains rare earth, by comprising the steps preparation:
(1) get commodity ZSM-5 molecular sieve, wherein in molar ratio,
SiO
2∶Al
2O
3＝50～120∶1
(2) preparation contains CeCl
3And LaCl
3The rare-earth salts acid solution, wherein press mass ratio,
CeCl
3∶LaCl
3＝1～3∶1
Under 80 ℃～120 ℃ temperature, above-mentioned commodity ZSM-5 molecular sieve was carried out ion-exchange 0.5～1.5 hour with above-mentioned rare-earth salts acid solution;
(3) to the molecular sieve filtration after the ion-exchange, under 400 ℃～600 ℃ temperature, roasting 2～4 hours;
Repetition (2), (3) step, reach 5%～25% of molecular sieve gross mass until rare earth oxide content; Obtain the described ZSM-5 molecular sieve crystal seed that contains rare earth.
7. according to the preparation method of the rare-earth-containing molecular sieve catalyst of the described modification of one of claim 5 to 6, it is characterized in that:
In the 1.2nd step, described inorganic acid is: phosphoric acid.
8. according to the preparation method of the rare-earth-containing molecular sieve catalyst of the described modification of one of claim 5 to 6, it is characterized in that:
In the 3.1st step, described metal oxide precursor is at least a in following: magnesium acetate, manganese acetate, manganese nitrate, magnesium dichloride, manganous chloride.
9. the rare-earth-containing molecular sieve catalyst of a modification is at preparation C
2～C
4Alkene in application, it is characterized in that:
Rare-earth-containing molecular sieve catalyst according to the modification of one of claim 1 to 4 is used for from methyl alcohol and/or dimethyl ether production C
2～C
4The reaction of alkene.
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| CN102211036B (en) * | 2010-04-09 | 2015-08-05 | 上海华谊（集团）公司 | A kind of modified molecular sieve catalyst and its precursor and preparation method thereof |
| EA024895B1 (en) * | 2011-12-19 | 2016-10-31 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Catalyst for preparing ethylene and propylene from methanol and/or dimethyl ether, preparation and use thereof |
| CN104437614B (en) * | 2013-09-24 | 2018-04-06 | 中国石油化工股份有限公司 | β cocrystallized molecular sieve catalysts of binderless ZSM-5 5/ and its production and use |
| CN104549437B (en) * | 2013-10-12 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of phosphorus and the rare earth modified molecular sieve catalysts of ZSM 5 and its preparation method and application |
| CN104549435B (en) * | 2013-10-12 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of rare earth modified molecular sieve catalysts of ZSM 5 and its preparation method and application |
| CN104923285A (en) * | 2014-03-21 | 2015-09-23 | 中石化洛阳工程有限公司 | Catalyst for preparing hydrocarbons from oxygen-containing compounds, and preparation method and application thereof |
| CN104307560B (en) * | 2014-10-20 | 2017-01-25 | 丁泳 | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst |
| CN106140266B (en) * | 2015-03-27 | 2019-09-13 | 中国石油大学(北京) | A kind of metal modified ZSM-5 molecular sieve catalyst and its preparation method and application |
| CN105439788B (en) * | 2015-12-10 | 2017-11-03 | 七台河宝泰隆煤化工股份有限公司 | A kind of method that olefine selective in product is improved in methanol-to-olefins reaction process |
| CN107398294B (en) * | 2016-05-18 | 2020-01-03 | 中国科学院大连化学物理研究所 | Preparation method and application of modified binder-free ZSM-11 molecular sieve catalyst |
| CN107970978B (en) * | 2016-10-21 | 2020-02-28 | 中国石油化工股份有限公司 | A kind of MFI structure molecular sieve containing phosphorus and loaded metal and preparation method thereof |
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