CN113877624A - Carbon tetraolefin skeleton normal structuring method and application thereof - Google Patents
Carbon tetraolefin skeleton normal structuring method and application thereof Download PDFInfo
- Publication number
- CN113877624A CN113877624A CN202010637111.9A CN202010637111A CN113877624A CN 113877624 A CN113877624 A CN 113877624A CN 202010637111 A CN202010637111 A CN 202010637111A CN 113877624 A CN113877624 A CN 113877624A
- Authority
- CN
- China
- Prior art keywords
- treatment
- hours
- catalyst
- acid
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 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 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- -1 carbon tetraene Chemical class 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 238000010306 acid treatment Methods 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 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
- 238000004898 kneading Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 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
- 230000008520 organization Effects 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 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
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 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
- 239000003795 chemical substances by application Substances 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
- 150000001336 alkenes Chemical group 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 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
Images
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 carbon tetraolefin skeleton normal structuring method. The method comprises the following steps: the method comprises the following steps of (1) carrying out contact reaction on a carbon tetraene and a skeleton normal structuring catalyst to generate n-butene, wherein the skeleton normal structuring 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 hydrogen when used for the normal structuring reaction of the carbon tetraolefin skeleton, and has good reaction activity, selectivity and stability. The method can convert isobutene into n-butene efficiently, continuously and stably.
Description
Technical Field
The invention relates to the field of carbon tetraene normal structuring, in particular to a carbon tetraene skeleton normal structuring method and application thereof.
Background
Industrial ethylene plants and refinery plants by-produce large amounts of carbon tetraolefins. The main components of the tetraolefins after butadiene extraction are isobutene and n-butene. Isobutene is one of important components of carbon tetraolefin, and is widely applied to the processes of synthesizing methyl tert-butyl ether (MTBE), butyl rubber, Methyl Methacrylate (MMA), polyisobutylene and the like. At present, the yield of isobutene in China per year exceeds 600 million tons; among them, synthesizing the gasoline additive MTBE with high octane number is the largest utilization way of isobutene, and more than 90% of isobutene is converted into MTBE to be added into a gasoline pool every year.
However, relevant ministries in China in 2017 propose that ethanol gasoline is pushed out comprehensively in 2020, and the content of other oxygen-containing compounds in the ethanol gasoline is regulated to be not higher than 0.5%, so MTBE cannot enter a gasoline pool. But the consumption of isobutene by downstream products such as butyl rubber, MMA and polyisobutylene is extremely limited.
The mono-olefins of butenes are divided into four, three n-butenes (1-butene, cis-2-butene and trans-2-butene) and one isobutene. Wherein, the 1-butene is used as an ethylene copolymer, can improve the product performance of the polyethylene and is an important basic chemical raw material; the 2-butylene is used as a raw material of alkylate oil and can replace isobutene to enter a gasoline pool, so that the problem of bulk utilization of isobutene is solved. Therefore, if isobutene can be converted into n-butene through normal formation, the method has scientific and economic significance.
Since isobutene has previously been considered to be more valuable than n-butene, the research direction and issued patents have focused on the skeletal isomerization of n-butene to isobutene. Fewer articles and patents have been reported and published for the orthosteric organization of the tetraolefin skeleton. And the tetraolefin skeleton normal structuring methods disclosed in the prior art generally employ an oxide-supported active metal component as the isobutylene normal structuring catalyst.
Disclosure of Invention
The invention provides a novel carbon tetraolefin skeleton normalization method aiming at the problems of poor carbon tetraolefin skeleton normalization reaction activity and frequent catalyst regeneration in the prior art. The method can convert isobutene into n-butene efficiently, continuously and stably.
To this end, the invention provides in a first aspect a method for orthosteric organization of a tetracarbon olefin skeleton, comprising the steps of:
enabling the carbon tetraene to contact and react with a skeleton normal structuring catalyst to generate n-butene; wherein the skeleton orthosteric catalyst comprises the following components in parts by weight:
1)10 to 50 parts of an amorphous binder,
2)50-90 parts of ZSM-35 molecular sieve.
According to some embodiments of the invention, the SiO of the ZSM-35 molecular sieve2/Al2O3The 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 SiO of the ZSM-35 molecular sieve2/Al2O3The molar ratio was 18. In other embodiments, the SiO of the ZSM-35 molecular sieve2/Al2O3The molar ratio was 20.
In the present invention, the diolefin refers to 1, 3-butadiene.
According to some embodiments of the invention, the ZSM-35 molecular sieve is a modified molecular sieve, the modification comprising an alkaline treatment and/or a steam treatment.
According to some embodiments of the invention, the modification comprises an alkaline treatment.
According to some embodiments of the invention, the modifying comprises steam treatment.
According to some embodiments of the invention, the modification comprises an alkali treatment and a water vapor treatment.
According to some embodiments of the invention, the alkali treatment temperature is 25 to 100 ℃, preferably 70 to 80 ℃ and in some embodiments, the alkali treatment temperature is 75 ℃.
According to some embodiments of the invention, the concentration of the alkali solution in the alkali treatment is 0.1 to 2mol/L, preferably 0.2 to 0.6mol/L, more preferably 0.25 to 0.5 mol/L. In some embodiments, the alkali solution concentration is 0.3 mol/L. In other embodiments, the alkali solution concentration is 0.4 mol/L.
According to some embodiments of the invention, the alkaline 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-.
According to some embodiments of the invention, the water vapor treatment volumetric space velocity is from 1 to 18 hours-1(ii) a Preferably 2 to 10 hours-1。
According to some embodiments of the invention, the water vapor treatment is carried out for a period of time ranging from 1 to 30 hours, preferably from 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 tetraolefin is isobutene or a mixed hydrocarbon containing isobutene, preferably the mixed hydrocarbon contains less than 1% by mass of diolefins. According to some embodiments of the present invention, the reaction temperature is 200-.
According to some embodiments of the invention, the reaction pressure is 0-1MPa, preferably 0-0.5MPa, more preferably 0-0.2MPa, e.g. 0.05MPa, 0.1MPa, 0.2 MPa.
According to some embodiments of the invention, the reaction volume space velocity is from 0.1 to 20 hours-1Preferably 0.5 to 15 hours-1More 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 orthosteric catalyst is prepared by a process comprising:
a) treating a ZSM-35 molecular sieve with alkali to obtain a precursor I;
b) kneading the precursor I obtained in the step a) and an amorphous binder for forming to obtain a precursor II;
c) carrying out steam treatment on the precursor II obtained in the step b) to obtain a skeleton normal catalyst;
according to some embodiments of the invention, the temperature of the alkaline treatment in step a) is between 25 and 100 ℃, preferably between 60 and 80 ℃. In some embodiments, the alkali treatment temperature is 75 ℃.
According to some embodiments of the invention, the concentration of the alkali solution in the alkali treatment in step a) is 0.1 to 2mol/L, preferably 0.2 to 0.6mol/L, more preferably 0.25 to 0.5 mol/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 base used for the alkali treatment is one or more selected from the group consisting 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 molded article is subjected to ammonium exchange after the kneading molding.
According to some embodiments of the present invention, the temperature of the water vapor treatment in step c) is 300-.
According to some embodiments of the invention, the water vapor treatment volume space velocity in step c) is from 1 to 18 hours-1Preferably 2 to 10 hours-1。
According to some embodiments of the invention, the water vapour treatment time in step c) is 1 to 30 hours, preferably 2 to 10 hours.
According to some preferred embodiments of the invention, in step c), an acid treatment modification step is further performed after the water vapor treatment.
According to some preferred embodiments of the present invention, in step c), the acid solution used for the acid treatment modification is one or more selected from nitric acid, citric acid, formic acid, and 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 acid solution concentration in the acid treatment is 0.1 to 2mol/L, preferably 0.2 to 0.4 mol/L. In some embodiments, the acid solution has a concentration of 0.3 mol/L.
According to some preferred embodiments of the invention, in step c), the acid treatment time is between 1 and 30 hours, preferably between 1 and 10 hours. In some embodiments, the acid treatment time is 2 hours.
According to some embodiments of the invention, the skeletal orthosteric catalyst is prepared by: the NaZSM-35 molecular sieve raw powder is roasted at the temperature of 500-550 ℃ for 4-6 hours to remove the template agent. And then treating the obtained material with sodium hydroxide alkali solution, filtering, drying, kneading and molding a binder, and drying and roasting. And (3) carrying out ammonium exchange, water washing and drying on the materials to obtain the ammonium type molecular sieve. And then carrying out steam treatment on the obtained molecular sieve material under normal pressure to obtain the steam modified molecular sieve. And (3) treating the steam-treated molecular sieve with an acid solution, filtering and drying to obtain the finished catalyst.
The second aspect of the invention also provides the use of a process according to the first aspect of the invention in the normal conversion of tetraolefins, preferably isobutene or mixed hydrocarbons containing isobutene, more preferably with a diolefin content of less than 1% by weight in the mixed hydrocarbons.
The invention adopts the ZSM-35 molecular sieve with two sets of pore canal systems of ten-membered ring and eight-membered ring, and can obtain higher linear chain olefin selectivity. The post-treatment modification method can adjust the acid density on the catalyst and clean the pore channel structure, and is favorable for the reaction stability of the catalyst. By adopting the method, isobutene reacts at the reaction temperature of 320-360 ℃, normal pressure and volume space velocity of 6 hours-1Can be converted into n-butene with the regeneration period of more than 750 hours, the average conversion rate of isobutene is 34.5 percent, and the average selectivity of n-butene is 94.5 percent. The reaction process does not need hydrogen, and the catalyst does not load metal components, so that the problems of poor reaction activity and frequent catalyst regeneration in the conventional industrial fixed bed device can be solved, and a better technical effect is achieved.
Drawings
FIG. 1 is a graph of the isobutene conversion and the n-butene selectivity as a function of time for example 1 according to 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 following examples.
The calculation formula of the n-butene yield in the embodiment of the invention is as follows:
mass yield of n-butene ═ wt (% by weight (trans-2-butene content + 1-butene content + cis-2-butene content)/(isobutylene content + trans-2-butene content + 1-butene content + cis-2-butene content + propylene content + normal oil content)
Example 1
The preparation method of the catalyst comprises the following steps: NaZSM-35 molecular sieve raw powder (SiO)2/Al2O3Ratio of 18) at 550 ℃ for 4 hours to remove the template agent, and the obtained materialAnd (3) carrying out alkali treatment on the material and 0.3mol/L NaOH at 75 ℃ for 2h, and carrying out suction filtration and drying to obtain the alkali modified molecular sieve. The material modified by the alkali treatment was mixed with alumina in a weight ratio of 1: 0.5. Adding a nitric acid solution into the mixture, kneading uniformly, extruding into strips, forming, drying, roasting, and then granulating. The resulting material was ammonium exchanged and then treated at 550 ℃ at a space velocity of 2 hours-1The obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at the temperature of 75 ℃, and the catalyst is obtained after suction filtration and drying.
Evaluation of catalyst Performance: isobutene with volume fraction of 40 percent is adopted as a raw material, the reaction pressure is 0.1MPa at the temperature of 330 ℃, and the liquid volume space velocity is 6 hours-1The catalyst activity was evaluated under the condition of a catalyst loading of 10mL, and the reaction results on the 5 th day of the catalyst are shown in Table 1. The results of the lifetime evaluation of the catalyst are shown in FIG. 1.
Example 2
The preparation method of the catalyst comprises the following steps: the difference from example 1 is only SiO in the molecular sieve2/Al2O3The ratio is 35.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 3
The preparation method of the catalyst comprises the following steps: the difference from example 1 is only SiO in the molecular sieve2/Al2O3The ratio is 45.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 4
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is that the NaOH concentration in the alkali treatment was 0.2mol/L as in example 1.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 5
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is that the NaOH concentration in the alkali treatment was 0.6mol/L as in example 1.
Evaluation of catalyst Performance: 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 is that the water vapor treatment temperature was 650 ℃.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 7
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is that the water vapor treatment temperature is 450 ℃ as in example 1.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 8
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is that the water vapor treatment temperature is 350 ℃ as in example 1.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Example 9
The preparation method of the catalyst comprises the following steps: the same as in example 1.
Evaluation of catalyst Performance: the only difference from example 1 is that the reaction temperature is 420 ℃ as in example 1. The results are shown in Table 1.
Example 10
The preparation method of the catalyst comprises the following steps: the same as in example 1.
Evaluation of catalyst Performance: the only difference from example 1 is that the reaction temperature is 250 ℃ as in example 1. The results are shown in Table 1.
Example 11
The preparation method of the catalyst comprises the following steps: the same as in example 1.
Evaluation of catalyst Performance: the only difference from example 1 is that the reaction temperature is 370 ℃ as in example 1. The results are shown in Table 1.
Example 12
The preparation method of the catalyst comprises the following steps: the same as in example 1.
Evaluation of catalyst Performance: 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: the same as in example 1.
Evaluation of catalyst Performance: in the same wayExample 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: the same as in example 1.
Evaluation of catalyst Performance: the difference from the 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: the same as in example 1.
Evaluation of catalyst Performance: the only difference from example 1 is that the reaction pressure is 0.05MPa, as in example 1. The results are shown in Table 1.
Example 16
The preparation method of the catalyst comprises the following steps: the same as in example 1.
Evaluation of catalyst Performance: the only difference from example 1 is that the reaction pressure is 0.2MPa, as in example 1. The results are shown in Table 1.
Example 17
The preparation method of the catalyst comprises the following steps: the only difference from example 1 is that the NaOH concentration in the alkali treatment was 0.2 mol/L.
Evaluation of catalyst Performance: 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 only difference from example 1 is that the NaOH concentration in the alkali treatment was 0.4 mol/L.
Evaluation of catalyst Performance: 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 sieve2/Al2O3The ratio is 20.
Evaluation of catalyst Performance: 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/Al2O3Ratio 18) was baked at 550 ℃ for 4 hours to remove the template. The resulting material was mixed with alumina in a 1:0.5 weight ratio. Adding a nitric acid solution into the mixture, kneading uniformly, extruding into strips, forming, drying, roasting, and then granulating. After ammonium exchange, drying and roasting the obtained material; and carrying out acid modification treatment on the obtained modified molecular sieve and 0.3mol/L citric acid at 75 ℃ for 2h, and carrying out suction filtration and drying to obtain the catalyst.
Evaluation of catalyst Performance: 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/Al2O3Ratio 18) was baked at 550 ℃ for 4 hours to remove the template. The resulting material was mixed with alumina in a 1:0.5 weight ratio. Adding a nitric acid solution into the mixture, kneading uniformly, extruding into strips, forming, drying, roasting, and then granulating. The resulting material was ammonium exchanged and then treated at 550 ℃ at a space velocity of 2 hours-1The obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at the temperature of 75 ℃, and the catalyst is obtained after suction filtration and drying.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Comparative example 3
Preparing a catalyst: NaZSM-35 molecular sieve raw powder (SiO)2/Al2O3Ratio 18) was baked at 550 ℃ for 4 hours to remove the template. And (3) carrying out alkali treatment on the obtained material and 0.3mol/L NaOH at 75 ℃ for 2h, and carrying out suction filtration and drying to obtain the alkali modified molecular sieve. The material modified by the alkali treatment was mixed with alumina in a weight ratio of 1: 0.5. Adding a nitric acid solution into the mixture, kneading uniformly, extruding into strips, forming, drying, roasting, and then granulating. And performing ammonium exchange on the obtained material, drying and roasting, performing acid modification treatment on the obtained modified molecular sieve and 0.3mol/L citric acid at 75 ℃ for 2h, performing suction filtration and drying to obtain the catalyst.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
Comparative example 4
The preparation method of the catalyst comprises the following steps: mixing NaY molecular sieve raw powder (SiO)2/Al2O3Ratio of 18) at 550 DEG CRoasting for 4 hours to remove the template agent. And (3) carrying out alkali treatment on the obtained material and 0.3mol/L NaOH at 75 ℃ for 2h, and carrying out suction filtration and drying to obtain the alkali modified molecular sieve. The material modified by the alkali treatment was mixed with alumina in a weight ratio of 1: 0.5. Adding a nitric acid solution into the mixture, kneading uniformly, extruding into strips, forming, drying, roasting, and then granulating. The resulting material was ammonium exchanged and then treated at 550 ℃ at a space velocity of 2 hours-1The obtained modified molecular sieve and 0.3mol/L citric acid are subjected to acid modification treatment for 2 hours at the temperature of 75 ℃, and the catalyst is obtained after suction filtration and drying.
Evaluation of catalyst Performance: the results are shown in Table 1, as in example 1.
TABLE 1
As can be seen from Table 1, when isobutene is contacted with the catalyst under different reaction conditions, the isobutene conversion rate of the catalyst prepared by using the modified ZSM-35 molecular sieve at 5 days of the reaction is greatly increased compared with the catalyst of the unmodified ZSM-35 molecular sieve, and the n-butene yield of the catalyst in example 1 is greatly increased compared with that of comparative examples 1-4.
As can be seen from FIG. 1, the method can continuously and stably convert isobutene into n-butene, and the isobutene conversion rate of the catalyst is more than 28% after the catalyst is operated for 30 days; the catalyst regeneration period is more than 750 hours, the average isobutene conversion rate is 34.5 percent, and the average n-butene selectivity is 94.5 percent. 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 variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A method of carbon tetraolefin skeletal orthosteric organization, comprising the steps of:
the method comprises the following steps of (1) carrying out contact reaction on a carbon tetraene and a skeleton normal structuring catalyst to generate n-butene, wherein the skeleton normal structuring catalyst comprises the following components in parts by weight:
1)10 to 50 parts of an amorphous binder,
2)50-90 parts of ZSM-35 molecular sieve.
2. The method of claim 1, wherein the ZSM-35 molecular sieve has SiO2/Al2O3The molar ratio is 15 to 300, preferably 15 to 50, more preferably 15 to 25; the mechanical strength of the framework positive catalyst is more than or equal to 5N/mm, preferably more than or equal to 6N/mm; and/or the carbon four-olefin is isobutene or mixed hydrocarbon containing isobutene, preferably the mass content of diolefin in the mixed hydrocarbon is less than 1 percent; and/or the amorphous binder is selected from one or more of alumina, boehmite, silica sol and water glass.
3. The process of claim 1 or 2, wherein the ZSM-35 molecular sieve is a modified molecular sieve, and wherein the modification comprises alkali treatment and/or steam treatment.
4. The method according to claim 3, wherein the temperature of the alkali treatment is 25-100 ℃, and/or the concentration of the alkali solution in the alkali treatment is 0.1-2mol/L, preferably 0.2-0.6mol/L, and/or the time of the alkali treatment is 1-30 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-1And/or the water vapor treatment time is 1 to 30 hours.
5. Process according to any one of claims 1 to 4, characterized in that the reaction temperature is 200-,and/or the volume space velocity of the reaction is 0.1 to 20 hours-1Preferably 0.5 to 15 hours-1More preferably 0.5 to 6 hours-1。
6. The method of any one of claims 1-5, wherein the skeletal orthosteric catalyst is prepared by a method comprising:
a) treating a ZSM-35 molecular sieve with alkali to obtain a precursor I;
b) kneading the precursor I obtained in the step a) and an amorphous binder for forming to obtain a precursor II;
c) and c) carrying out steam treatment on the precursor II obtained in the step b) to obtain the skeleton normal catalyst.
7. The method according to claim 6, wherein the alkali solution used in the alkali treatment in step a) is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide and calcium hydroxide, preferably the temperature of the alkali treatment is 25 to 100 ℃, and/or the concentration of the alkali solution in the alkali treatment is 0.1 to 2mol/L, preferably 0.2 to 0.6mol/L, and/or the time of the alkali treatment is 1 to 30 hours.
8. The process according to claim 6 or 7, characterized in that in step c) the temperature of the steam treatment is 300--1And/or the water vapor treatment time is 1 to 30 hours.
9. The method according to any one of claims 6 to 8, further comprising an acid treatment modification step after the water vapor treatment in step c), wherein the acid solution used in the acid treatment is one or more selected from nitric acid, citric acid, oxalic acid or formic acid, preferably the acid treatment temperature is 25 to 100 ℃, and/or the concentration of the acid solution used in the acid treatment is 0.1 to 2mol/L, and/or the time of the acid treatment is 1 to 30 hours.
10. Use of a process according to any one of claims 1 to 9 in the skeletal ortho-conversion of a tetraolefin, preferably isobutene or mixed hydrocarbons containing isobutene, more preferably with a diolefin content of less than 1% by mass in the mixed hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010637111.9A CN113877624B (en) | 2020-07-03 | 2020-07-03 | Method for orthogonalization of carbon tetraolefin skeleton and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010637111.9A CN113877624B (en) | 2020-07-03 | 2020-07-03 | Method for orthogonalization of carbon tetraolefin skeleton and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113877624A true CN113877624A (en) | 2022-01-04 |
| CN113877624B CN113877624B (en) | 2024-01-26 |
Family
ID=79011950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010637111.9A Active CN113877624B (en) | 2020-07-03 | 2020-07-03 | Method for orthogonalization of carbon tetraolefin skeleton and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113877624B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994008920A1 (en) * | 1992-10-16 | 1994-04-28 | Mobil Oil Corporation | Olefin skeletal isomerization process using zsm-35 |
| US20130204057A1 (en) * | 2010-03-15 | 2013-08-08 | Total Research & Technology Feluy | Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts |
| CN105983435A (en) * | 2015-03-03 | 2016-10-05 | 卓润生 | Butane isomerization catalyst and preparation method and application thereof |
| CN107286983A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN107286984A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of n-butene gasoline component coproduction isobutene |
| CN108530254A (en) * | 2018-04-25 | 2018-09-14 | 陈久仓 | A method of mixing carbon four prepares normal butane |
| CN110385142A (en) * | 2019-07-19 | 2019-10-29 | 河北工业大学 | Anti- applications catalyst of a kind of positive structureization of iso-butane and its preparation method and application |
-
2020
- 2020-07-03 CN CN202010637111.9A patent/CN113877624B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994008920A1 (en) * | 1992-10-16 | 1994-04-28 | Mobil Oil Corporation | Olefin skeletal isomerization process using zsm-35 |
| US20130204057A1 (en) * | 2010-03-15 | 2013-08-08 | Total Research & Technology Feluy | Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts |
| CN105983435A (en) * | 2015-03-03 | 2016-10-05 | 卓润生 | Butane isomerization catalyst and preparation method and application thereof |
| CN107286983A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN107286984A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of n-butene gasoline component coproduction isobutene |
| CN108530254A (en) * | 2018-04-25 | 2018-09-14 | 陈久仓 | A method of mixing carbon four prepares normal butane |
| CN110385142A (en) * | 2019-07-19 | 2019-10-29 | 河北工业大学 | Anti- applications catalyst of a kind of positive structureization of iso-butane and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 仉涛 等: "ZSM-35分子筛催化剂催化正丁烯骨架异构工艺条件研究", 广州化工, vol. 42, no. 23, pages 83 - 86 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113877624B (en) | 2024-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103301876B (en) | A kind of preparation method of straight-chain olefin skeleton isomerization catalyst | |
| JP2006514085A (en) | Method for producing dimethyl ether from methanol | |
| CN105983435B (en) | A kind of isomerization of butene catalyst and its preparation method and application | |
| WO2014123243A1 (en) | Olefin oligomerization method and catalyst used in same | |
| CN113877624A (en) | Carbon tetraolefin skeleton normal structuring method and application thereof | |
| JP6446033B2 (en) | Process for producing unsaturated hydrocarbons | |
| CN103861644B (en) | A kind of modified clay Catalysts and its preparation method for deolefination | |
| CN108114735B (en) | Preparation method of linear olefin skeletal isomerization catalyst | |
| CN105597842B (en) | The renovation process of ethylbenzene catalyst | |
| CN107286983B (en) | The method of C 4 olefin oligomerisation gasoline component | |
| CN113117729B (en) | Isomerization catalyst and method for preparing same | |
| CN112742456B (en) | Dehydrogenation cracking catalyst, preparation method thereof and method for producing ethylene and propylene by using carbon tetrahydrocarbon | |
| CN114054070B (en) | Solid acid catalyst, preparation method thereof and alkylation reaction method | |
| CN109370646B (en) | Catalytic cracking gasoline desulfurization modification method | |
| CN105712818B (en) | A kind of method that MTBE and TBA compounds prepare isobutene | |
| CN104109071B (en) | The method of cracked C 5 fraction propylene | |
| CN107267200B (en) | A method of it is alkylated by alkane and alkene | |
| CN1123387C (en) | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof | |
| CN105665038B (en) | Inactivate the renovation process of ethylbenzene catalyst | |
| CN107286984B (en) | The method of n-butene gasoline component coproduction isobutene | |
| CN104557380B (en) | The method that extracting carbon four produces propylene | |
| CN115716651B (en) | ZSM-35 molecular sieve and preparation method thereof, isomerization catalyst and preparation method thereof, and isomerization method | |
| CN106431810B (en) | Method for preparing isoamylene by n-pentene skeletal isomerization | |
| CN107286985B (en) | The method of C 4 olefin gasoline component coproduction ethylene or propylene | |
| CN112742445A (en) | Selective hydrogenation molecular sieve material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |