CN113877624B - Method for orthogonalization of carbon tetraolefin skeleton and application thereof - Google Patents
Method for orthogonalization of carbon tetraolefin skeleton and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 238000010306 acid treatment Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000002746 orthostatic effect Effects 0.000 claims 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005755 formation reaction Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
Abstract
The invention provides a method for orthogonalization of a carbon tetraolefin skeleton. The method comprises the following steps: contacting and reacting carbon tetraolefin and a framework orthosteric catalyst to generate n-butene, wherein the framework orthosteric catalyst comprises the following components in parts by weight: a) 10-50 parts of amorphous binder, b) 50-90 parts of ZSM-35 molecular sieve. The catalyst does not load metal components, does not need to be subjected to hydrogenation when being used for the normal formation reaction of the carbon tetraolefin skeleton, and has good reaction activity, selectivity and stability. The method can convert isobutene into normal butene with high efficiency, continuously and stably.
Description
Technical Field
The invention relates to the field of orthogonalization of carbon tetraolefins, in particular to a orthogonalization method of a carbon tetraolefin skeleton and application thereof.
Background
Industrial ethylene plants and refinery plants produce large amounts of carbon tetraolefins as by-products. The main components of the carbon tetraolefins after butadiene extraction are isobutylene and normal butenes. Isobutene is one of the important components of carbon tetraolefins and is widely applied to the processes of synthesizing Methyl Tertiary Butyl Ether (MTBE), butyl rubber, methyl Methacrylate (MMA), polyisobutene and the like. At present, the annual isobutene yield of China exceeds 600 ten thousand tons; among them, the synthesis of high-octane gasoline additive MTBE is the most largely utilized route of isobutene, and more than 90% of isobutene is converted into MTBE and added into gasoline pool each year.
However, the relevant ministry of China in 2017 proposes that ethanol gasoline is comprehensively pushed in 2020, and the content of other oxygen-containing compounds in the ethanol gasoline is regulated not to be higher than 0.5%, so MTBE cannot enter a gasoline pool. While the consumption of isobutene by downstream products such as butyl rubber, MMA and polyisobutene is extremely limited.
The mono-olefins of butene are classified into four kinds, three kinds of n-butene (1-butene, cis-2-butene and trans-2-butene) and one kind of isobutylene. Wherein, 1-butene is used as an ethylene copolymer, which can improve the product performance of polyethylene and is an important basic chemical raw material; 2-butene is used as a raw material of the alkylate, and can replace isobutene to enter a gasoline pool, so that the problem of bulk utilization of isobutene is solved. Therefore, if isobutene is converted into normal butene through normal structuring, the method has scientific and economic significance.
Since isobutene has been considered to be of higher value than n-butene, research and published patents have focused on skeletal isomerization of n-butene to produce isobutene. Few articles and patents have been reported and disclosed for orthogonalization of the carbon tetraolefin backbone. And the method for orthogonalization of the carbon tetraolefin skeleton disclosed in the prior art generally adopts an oxide-loaded active metal component as an isobutene orthogonalization catalyst.
Disclosure of Invention
Aiming at the problems of poor orthosteric reaction activity and frequent catalyst regeneration of the carbon tetraolefin skeleton in the prior art, the invention provides a novel orthosteric method of the carbon tetraolefin skeleton. The method can convert isobutene into normal butene with high efficiency, continuously and stably.
To this end, a first aspect of the present invention provides a method for orthogonalization of a carbon tetraolefin backbone, comprising the steps of:
enabling the carbon tetraolefin and the framework orthosteric catalyst to react in a contact way to generate n-butene; wherein the skeleton orthoconstituted catalyst comprises the following components in parts by weight:
1) 10-50 parts of an amorphous binder,
2) 50-90 parts of ZSM-35 molecular sieve.
According to some embodiments of the invention, the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 15 to 300, preferably 15 to 50, more preferably 15 to 25; the mechanical strength of the catalyst is more than or equal to 5N/mm, preferably more than or equal to 6N/mm. In some embodiments, the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio was 18. In other embodiments, the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio was 20.
The diolefin in the present invention refers to 1, 3-butadiene.
According to some embodiments of the invention, the ZSM-35 molecular sieve is a modified molecular sieve, the modification including a base treatment and/or a water vapor treatment.
According to some embodiments of the invention, the modification comprises alkali treatment.
According to some embodiments of the invention, the modifying comprises steam treatment.
According to some embodiments of the invention, the modification comprises alkali treatment and steam treatment.
According to some embodiments of the invention, the alkali treatment temperature is 25-100 ℃, preferably 70-80 ℃ and in some examples, 75 ℃.
According to some embodiments of the invention, the alkali solution concentration in the alkali treatment is 0.1-2mol/L, preferably 0.2-0.6mol/L, more preferably 0.25-0.5mol/L. In some embodiments, the alkali solution concentration is 0.3mol/L. In other embodiments, the alkali solution concentration is 0.4mol/L.
According to some embodiments of the invention, the alkali treatment time is 1 to 30 hours, preferably 2 to 10 hours.
According to some embodiments of the invention, the water vapor treatment temperature is 300-600 ℃, e.g., 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃.
According to some embodiments of the invention, the water vapor treatment volume space velocity is from 1 to 18 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 2-10 hours -1 。
According to some embodiments of the invention, the water vapor treatment time is 1 to 30 hours, preferably 2 to 10 hours.
According to some embodiments of the invention, the amorphous binder is selected from one or more of alumina, boehmite, silica sol and water glass.
According to some embodiments of the invention, the carbon tetraolefin is isobutylene or a mixed hydrocarbon containing isobutylene, preferably the mixed hydrocarbon has a diolefin mass content of less than 1%. According to some embodiments of the invention, the reaction temperature is 200-500 ℃, preferably 300-450 ℃, such as 300 ℃, 330 ℃, 360 ℃, 390 ℃, 420 ℃, 450 ℃.
According to some embodiments of the invention, the reaction pressure is 0-1MPa, preferably 0-0.5MPa, more preferably 0-0.2MPa, for example 0.05MPa, 0.1MPa, 0.2MPa.
According to some embodiments of the invention, the reaction volume space velocity is from 0.1 to 20 hours -1 Preferably 0.5 to 15 hours -1 More preferably 0.5 to 6 hours -1 . In some embodiments, the reaction volume space velocity is 2 hours -1 . In some embodiments, the reaction volume space velocity is 4 hours -1 . In other embodiments, the reaction volume space velocity is 6 hours -1 。
According to some embodiments of the invention, the skeletal orthogonalization catalyst is prepared by a method comprising the steps of:
a) Performing alkali treatment on the ZSM-35 molecular sieve to obtain a precursor I;
b) Kneading and molding the precursor I obtained in the step a) and an amorphous binder to obtain a precursor II;
c) Carrying out steam treatment on the precursor II obtained in the step b) to obtain a skeleton orthosteric catalyst;
according to some embodiments of the invention, the temperature of the alkali treatment in step a) is 25-100 ℃, preferably 60-80 ℃. In some embodiments, the alkali treatment temperature is 75 ℃.
According to some embodiments of the invention, the concentration of the alkaline solution in the alkaline treatment in step a) is between 0.1 and 2mol/L, preferably between 0.2 and 0.6mol/L, more preferably between 0.25 and 0.5mol/L.
According to some embodiments of the invention, the time of the alkaline treatment in step a) is 1 to 30 hours, preferably 2 to 10 hours.
According to some embodiments of the invention, in step a), the alkali used for the alkali treatment is selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
According to some embodiments of the invention, in step a), the ZSM-35 molecular sieve is an alkali metal ZSM-35 molecular sieve. In some embodiments, the ZSM-35 molecular sieve is a NaZSM-35 molecular sieve.
According to some embodiments of the invention, in step a), the ZSM-35 molecular sieve is first calcined to remove the templating agent.
According to some embodiments of the invention, in step b), the amorphous binder is selected from one or more of alumina, boehmite, silica sol and water glass.
According to some embodiments of the invention, in step b), the shaped article is subjected to an ammonium exchange after kneading shaping.
According to some embodiments of the invention, the water vapor treatment temperature in step c) is 300-600 ℃, e.g. 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃.
According to some embodiments of the invention, the water vapor treatment volume space velocity in step c) is from 1 to 18 hours -1 Preferably 2-10 hours -1 。
According to some embodiments of the invention, the water vapour treatment time in step c) is from 1 to 30 hours, preferably from 2 to 10 hours.
According to some preferred embodiments of the invention, in step c), an acid treatment modification step is also carried out after the water vapor treatment.
According to some preferred embodiments of the invention, in step c), the acid solution used for the acid treatment modification is selected from one or more of nitric acid, citric acid, formic acid or oxalic acid.
According to some preferred embodiments of the invention, in step c), the acid treatment temperature is between 10 and 100 ℃, preferably between 70 and 80 ℃. In some embodiments, the acid treatment temperature is 75 ℃.
According to some preferred embodiments of the invention, in step c) the concentration of the acid solution in the acid treatment is between 0.1 and 2mol/L, preferably between 0.2 and 0.4mol/L. In some embodiments, the acid solution concentration is 0.3mol/L.
According to some preferred embodiments of the invention, in step c), the acid treatment is carried out for a time of 1 to 30 hours, preferably 1 to 10 hours. In some embodiments, the acid treatment time is 2 hours.
According to some embodiments of the invention, the method for preparing the skeletal orthoconstituted catalyst comprises: roasting NaZSM-35 molecular sieve raw powder at 500-550 ℃ for 4-6 hours to remove the template agent. And then the obtained material is treated by sodium hydroxide alkali solution, filtered, dried, kneaded and molded by the binder, dried and roasted. And (3) carrying out ammonium exchange, water washing and drying on the materials to obtain the ammonium molecular sieve. And then carrying out steam treatment on the molecular sieve material under normal pressure to obtain the steam modified molecular sieve. The water vapor treatment molecular sieve is treated by acid solution, filtered and dried to obtain the finished catalyst.
In a second aspect the invention also provides the use of a process according to the first aspect of the invention in the normal reaction of a carbon tetraolefin, preferably the carbon tetraolefin is isobutylene or a mixed hydrocarbon containing isobutylene, more preferably the mixed hydrocarbon has a diolefin mass content of less than 1%.
The invention adopts ZSM-35 molecular sieve with ten-membered ring and eight-membered ring two sets of pore systems, and can obtain higher linear olefin selectivity. The post-treatment modification method used can regulate the catalystAcid density and cleaning pore canal structure, which is favorable for the reaction stability of the catalyst. The method is adopted to make isobutene at the reaction temperature of 320-360 ℃, normal pressure and volume space velocity for 6 hours -1 The regeneration period may be greater than 750 hours with an average isobutene conversion of 34.5% and an average n-butene selectivity of 94.5%. The reaction process does not need to be in hydrogen, the catalyst does not load metal components, the problems of poor reaction activity and frequent catalyst regeneration in the existing industrial fixed bed device can be relieved, and a better technical effect is achieved.
Drawings
FIG. 1 is a graph showing the conversion of isobutene and the selectivity to normal butene as a function of time for example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the scope disclosed in the examples below.
The calculation formula of the n-butene yield in the embodiment of the invention is as follows:
normal butene mass yield wt% = (trans-2-butene content+1-butene content+cis-2-butene content)/(isobutene content+trans-2-butene content+1-butene content+cis-2-butene content+propylene content+normal structured oil content)
Example 1
The preparation method of the catalyst comprises the following steps: naZSM-35 molecular sieve raw powder (SiO) 2 /Al 2 O 3 The ratio is 18), the template agent is removed by roasting at 550 ℃ for 4 hours, the obtained material is treated with 0.3mol/L NaOH for 2 hours at 75 ℃, and the alkali modified molecular sieve is obtained by suction filtration and drying. The alkali-treated modified material was mixed with alumina in a 1:0.5 weight ratio. Adding nitric acid solution into the mixture, kneading, extruding, drying, calcining, and granulating. The obtained material was subjected to ammonium exchange at 550℃and space velocity for 2 hours -1 The modified molecular sieve is treated by water vapor for 2 hours under the condition that the obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at 75 ℃, and the catalyst is obtained by suction filtration and drying.
Catalyst performance evaluation: isobutene containing 40% of isobutane by volume fraction is used as a raw material, and the reaction pressure is 0.1MPa at the temperature of 330 ℃ and the liquid volume space velocity is 6 hoursTime of day -1 The catalyst activity was evaluated at a catalyst loading of 10mL, and the reaction results at the 5 th day of the catalyst are shown in Table 1. The results of the catalyst life evaluation are shown in FIG. 1.
Example 2
The preparation method of the catalyst comprises the following steps: as in example 1, the only difference from example 1 is the SiO in the molecular sieve 2 /Al 2 O 3 The ratio was 35.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 3
The preparation method of the catalyst comprises the following steps: as in example 1, the only difference from example 1 is the SiO in the molecular sieve 2 /Al 2 O 3 The ratio was 45.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 4
The preparation method of the catalyst comprises the following steps: as in example 1, the difference from example 1 was only that the NaOH concentration in the alkali treatment was 0.2mol/L.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 5
The preparation method of the catalyst comprises the following steps: as in example 1, the difference from example 1 was only that the NaOH concentration in the alkali treatment was 0.6mol/L.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 6
The preparation method of the catalyst comprises the following steps: the only difference from example 1 was that the water vapor treatment temperature was 650 ℃.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 7
The preparation method of the catalyst comprises the following steps: the difference from example 1 was only that the water vapor treatment temperature was 450℃as in example 1.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 8
The preparation method of the catalyst comprises the following steps: the difference from example 1 was only that the water vapor treatment temperature was 350℃as in example 1.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Example 9
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the only difference from example 1 is that the reaction temperature was 420 ℃. The results are shown in Table 1.
Example 10
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the only difference from example 1 is that the reaction temperature was 250 ℃. The results are shown in Table 1.
Example 11
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: the difference from example 1 was only that the reaction temperature was 370℃as in example 1. The results are shown in Table 1.
Example 12
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the difference from example 1 is only that the liquid mass space velocity is 2h -1 . The results are shown in Table 1.
Example 13
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the difference from example 1 is only that the liquid volume space velocity is 4h -1 . The results are shown in Table 1.
Example 14
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the difference from example 1 is only that the liquid volume space velocity is 8h -1 . The results are shown in Table 1.
Example 15
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the difference from example 1 was only that the reaction pressure was 0.05MPa. The results are shown in Table 1.
Example 16
The preparation method of the catalyst comprises the following steps: as in example 1.
Catalyst performance evaluation: as in example 1, the difference from example 1 was only that the reaction pressure was 0.2MPa. The results are shown in Table 1.
Example 17
The preparation method of the catalyst comprises the following steps: the difference from example 1 is only that the NaOH concentration in the alkali treatment is 0.2mol/L.
Catalyst performance evaluation: the only difference from example 1 is that the acid used in the acid modification treatment was nitric acid, and the results are shown in Table 1.
Example 18
The preparation method of the catalyst comprises the following steps: the difference from example 1 is only that the NaOH concentration in the alkali treatment is 0.4mol/L.
Catalyst performance evaluation: the only difference from example 1 is that the acid used in the acid modification treatment was oxalic acid, and the results are shown in Table 1.
Example 19
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is the SiO in the molecular sieves 2 /Al 2 O 3 The ratio was 20.
Catalyst performance evaluation: the only difference from example 1 is that the acid used in the acid modification treatment was formic acid, and the results are shown in Table 1.
Comparative example 1
The preparation method of the catalyst comprises the following steps: naZSM-35 molecular sieve raw powder (SiO) 2 /Al 2 O 3 Ratio 18) was calcined at 550 c for 4 hours to remove the templating agent. The resulting material was mixed with alumina in a 1:0.5 weight ratio. Adding nitric acid solution into the mixture, kneading, extruding, drying, calcining, and granulating. The obtained material is dried and roasted after ammonium exchange; the obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at 75 ℃, and the catalyst is obtained through suction filtration and drying.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Comparative example 2
The preparation method of the catalyst comprises the following steps: naZSM-35 molecular sieve raw powder (SiO) 2 /Al 2 O 3 Ratio 18) was calcined at 550 c for 4 hours to remove the templating agent. The resulting material was mixed with alumina in a 1:0.5 weight ratio. Adding nitric acid solution into the mixture, kneading, extruding, drying, calcining, and granulating. The obtained material was subjected to ammonium exchange at 550℃and space velocity for 2 hours -1 The modified molecular sieve is treated by water vapor for 2 hours under the condition that the obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at 75 ℃, and the catalyst is obtained by suction filtration and drying.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Comparative example 3
And (3) preparing a catalyst: naZSM-35 molecular sieve raw powder (SiO) 2 /Al 2 O 3 Ratio 18) was calcined at 550 c for 4 hours to remove the templating agent. And (3) carrying out alkali treatment on the obtained material and 0.3mol/L NaOH for 2 hours at the temperature of 75 ℃, and carrying out suction filtration and drying to obtain the alkali modified molecular sieve. The alkali-treated modified material was mixed with alumina in a 1:0.5 weight ratio. Adding nitric acid solution into the mixture, kneading, extruding, drying, calcining, and granulating. And (3) carrying out ammonium exchange on the obtained material, drying and roasting, carrying out acid modification treatment on the obtained modified molecular sieve and 0.3mol/L citric acid for 2 hours at 75 ℃, and carrying out suction filtration and drying to obtain the catalyst.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
Comparative example 4
The preparation method of the catalyst comprises the following steps: the NaY molecular sieve raw powder (SiO) 2 /Al 2 O 3 Ratio 18) was calcined at 550 c for 4 hours to remove the templating agent. And (3) carrying out alkali treatment on the obtained material and 0.3mol/L NaOH for 2 hours at the temperature of 75 ℃, and carrying out suction filtration and drying to obtain the alkali modified molecular sieve. The alkali-treated modified material was mixed with alumina in a 1:0.5 weight ratio. Adding nitric acid solution into the mixture, kneading, extruding, drying, calcining, and granulating. The obtained material was subjected to ammonium exchange at 550℃and space velocity for 2 hours -1 The modified molecular sieve is treated by water vapor for 2 hours under the condition that the obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at 75 ℃, and the catalyst is obtained by suction filtration and drying.
Catalyst performance evaluation: the results are shown in Table 1, as in example 1.
TABLE 1
As can be seen from Table 1, contacting isobutylene with the catalyst under different reaction conditions greatly increased the conversion of isobutylene at reaction day 5 of the catalyst prepared with the modified ZSM-35 molecular sieve compared to the unmodified ZSM-35 molecular sieve catalyst, and the yield of n-butene of the catalyst of example 1 was greatly increased compared to comparative examples 1-4.
As can be seen from FIG. 1, the isobutene can be continuously and stably converted into normal butene by adopting the method, and the isobutene conversion rate is more than 28% after the catalyst is operated for 30 days; the catalyst regeneration period was greater than 750 hours, the average isobutene conversion was 34.5% and the average normal butene selectivity was 94.5%. Has better industrial application prospect.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (22)
1. A method for orthogonalization of a carbon tetraolefin backbone comprising the steps of:
contacting and reacting carbon tetraolefin and a framework orthosteric catalyst to generate n-butene, wherein the framework orthosteric catalyst comprises the following components in parts by weight:
1) 10-50 parts of an amorphous binder,
2) 50-90 parts of ZSM-35 molecular sieve,
wherein the amorphous binder is one or more than two of alumina, boehmite, silica sol and water glass,
wherein the ZSM-35 molecular sieve is modifiedA molecular sieve, said modification comprising an alkali treatment and a water vapor treatment, said alkali treatment being at a temperature of from 25 to 100 ℃, and/or said alkali treatment having an alkali solution concentration of from 0.1 to 2mol/L, and/or said alkali treatment being for a period of from 1 to 30 hours; the temperature of the water vapor treatment is 300-600 ℃ and/or the volume space velocity of the water vapor treatment is 1-18 hours -1 And/or the water vapor treatment time is 1-30 hours,
wherein the reaction temperature is 300-500 ℃, and/or the reaction pressure is 0.05-1MPa, and/or the volume space velocity of the reaction is 0.1-20 hours -1 。
2. The method of claim 1, wherein the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 15-300; the mechanical strength of the skeleton orthoconstituted catalyst is more than or equal to 5N/mm; and/or the carbon tetraolefin is isobutene or a mixed hydrocarbon containing isobutene.
3. The method of claim 1, wherein the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 15-50.
4. The method of claim 1, wherein the ZSM-35 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 15-25.
5. The method of claim 1, wherein the mechanical strength of the skeletal orthostatic catalyst is greater than or equal to 6N/mm.
6. The method according to claim 2, wherein the diolefin mass content in the mixed hydrocarbon is less than 1%.
7. The method according to claim 1, wherein the alkali solution concentration in the alkali treatment is 0.2-0.6 mol/L.
8. The method according to any one of claims 1 to 7, wherein the reaction temperature is 300 to 450 ℃.
9. The process according to any one of claims 1 to 7, wherein the reaction pressure is 0.05 to 0.5 MPa.
10. The method according to any one of claims 1 to 7, wherein the reaction pressure is 0.05 to 0.2Mpa.
11. The process according to any one of claims 1 to 7, wherein the volumetric space velocity of the reaction is from 0.5 to 15 hours -1 。
12. The process according to any one of claims 1 to 7, wherein the volumetric space velocity of the reaction is from 0.5 to 6 hours -1 。
13. The method according to any one of claims 1 to 7, wherein the skeletal orthostatic catalyst is prepared by a process comprising the steps of:
a) Performing alkali treatment on the ZSM-35 molecular sieve to obtain a precursor I;
b) Kneading and molding the precursor I obtained in the step a) and an amorphous binder to obtain a precursor II;
c) And b) carrying out steam treatment on the precursor II obtained in the step b) to obtain the skeleton orthostatic catalyst.
14. The method according to claim 13, wherein the alkali solution used in the alkali treatment in step a) is selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
15. The method according to claim 13, characterized in that the temperature of the alkali treatment in step a) is 25-100 ℃, and/or the alkali concentration in the alkali treatment is 0.1-2mol/L, and/or the time of the alkali treatment is 1-30 hours.
16. The method according to claim 13, wherein the alkali solution concentration in the alkali treatment in step a) is 0.2-0.6 mol/L.
17. The process according to claim 13, wherein in step c) the temperature of the water vapour treatment is 300-600 ℃ and/or the volume space velocity of the water vapour treatment is 1-18 hours -1 And/or the water vapor treatment time is 1-30 hours.
18. The method according to claim 13, wherein the water vapor treatment in step c) is followed by an acid treatment modification step, wherein the acid solution used in the acid treatment is one or more selected from nitric acid, citric acid, oxalic acid and formic acid.
19. The method according to claim 18, wherein the acid treatment temperature is 25-100 ℃, and/or the acid solution concentration used in the acid treatment is 0.1-2mol/L, and/or the acid treatment time is 1-30 hours.
20. Use of the method of any one of claims 1-19 in a carbon-tetraolefin skeletal orthogonalization reaction.
21. The use according to claim 20, wherein the carbon tetraolefin is isobutylene or a mixed hydrocarbon containing isobutylene.
22. The use according to claim 21, wherein the diolefin mass content in the mixed hydrocarbon is less than 1%.
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