CN108014845A - A kind of catalyst for being catalyzed butane production isobutene and its application - Google Patents
A kind of catalyst for being catalyzed butane production isobutene and its application Download PDFInfo
- Publication number
- CN108014845A CN108014845A CN201610956172.5A CN201610956172A CN108014845A CN 108014845 A CN108014845 A CN 108014845A CN 201610956172 A CN201610956172 A CN 201610956172A CN 108014845 A CN108014845 A CN 108014845A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- catalyst bed
- catalytic component
- reaction
- butane
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 84
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000001273 butane Substances 0.000 title claims abstract description 34
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 230000003197 catalytic effect Effects 0.000 claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 claims abstract description 35
- 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 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011368 organic material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 23
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 235000013844 butane Nutrition 0.000 abstract description 33
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 7
- 241000269350 Anura Species 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 18
- 238000006317 isomerization reaction Methods 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 235000013847 iso-butane Nutrition 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 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
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- -1 methyl tertbutyl Chemical group 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of catalyst for being catalyzed butane production isobutene and its application, the catalyst includes catalytic component a and catalytic component b, the catalytic component a is 11 molecular sieve catalysts of SAPO of carried metal element, and the catalytic component b is by olefin-containing organic materials dipping and 11 molecular sieves of dried SAPO.The method of catalysis butane production isobutene provided by the invention uses the catalyst, improves butanes conversion and selective isobutene, and reduce the generation of C8 accessory substances.
Description
Technical field
The present invention relates to the technical field that alkene is prepared by alkane, and in particular to one kind is used to be catalyzed butane production isobutene
Catalyst, the catalyst isobutene production in application, and it is a kind of be catalyzed butane production isobutene method.
Background technology
Isobutene is the important monomer of synthetic rubber and resin, and important fine chemical material, in chemical industry
It is widely used.The source of isobutene is mainly the C_4 hydrocarbon class that catalytic cracking produces, wherein in addition to olefins also containing a large amount of positive fourths
Alkane and iso-butane.Iso-butane not only can produce isobutene with dehydrogenation, and propylene oxide and methyl tertbutyl are produced with propylene cooxidation
Ether, can also produce high-knock rating gasoline by alkylated reaction with n-butene, have a preferable economic value, therefore by positive fourth
This process route of alkane skeletal isomerization production iso-butane increasingly attracts attention.In addition, in suitable catalyst and technique bar
, can also be from the direct step production isobutene of normal butane under part, relatively firstly generating iso-butane, dehydrogenation produces isobutene more again
For simplicity, and the hot spot studied recently.
The molecular sieve or composite oxides of carried noble metal Pt, Pd are the most commonly used normal butane heterogeneous catalysts, wherein
SAPO-11 molecular sieves are to apply more carrier.The skeleton of aluminium silicophosphate molecular sieve SAPO-11 is by Si, P, Al and O element structure
Into its structure belongs to the AEL type structures of international zeolite association name.SAPO-11 molecular sieves have one-dimensional ten-ring channel system,
Duct is ellipse, freely a diameter of 0.65 × 0.40 nanometer, belongs to rhombic system, and unit cell dimension is a=1.35 nanometers, b=
1.85 nanometers, c=0.84 nanometers.Due in the skeleton structure of SAPO-11 molecular sieves there are Si-O-Al connections, so this point
Sub- sifter device has acidity.At present, SAPO-11 molecular sieves catalytic cracking, be hydrocracked, isomerization, the alkyl with side chain aromatic hydrocarbons
A variety of oil refining such as change, isomerization dewaxing and light olefin polymerization are with widely being studied or being applied in chemical engineering industry.
Borosilicate zeolite loaded Pt catalyst is applied to normal butane isomerization reaction, the conversion ratio of normal butane by US 4433190
For 38%, selective isobutene reaches 28%.CN 1504261A using dipping, exchange or blending by the way of by metal active into
Share and being loaded on SAPO molecular sieve, and as the catalyst of normal butane preparing isobutene, selective isobutene is up to 35%.It is although existing
These researchs having achieve certain achievement, but will also realize that from above-mentioned document, and simple bifunctional catalyst is used for positive fourth
During alkane isomerization, the yield of isobutene is than relatively low.Meanwhile, it is capable to n-butane conversion and the isobutene selection of higher are obtained at the same time
Property be in this area always constantly pursue.
The content of the invention
It is an object of the invention to provide a kind of catalyst for being used to be catalyzed butane production isobutene, the catalyst is different
Application in butylene production, and the method using catalyst butane production isobutene.Urged using provided by the invention
Agent or method, can not only improve isobutene yield, but also reduce the generation of C8 accessory substances, extend the use of catalyst
Service life.
The catalyst of catalysis butane production isobutene provided by the invention includes catalytic component a and catalytic component b, institute
The SAPO-11 molecular sieves that catalytic component a is carried metal element are stated, the catalytic component b is by olefin-containing organic matter
Material dipping and dried SAPO-11 molecular sieves.
According to the preferred embodiment of the present invention, the olefin-containing organic materials includes alkene and/or ethers.The alkene
It is preferably selected from C7-C12 alkene, preferably C6-C10 alkene, more preferably C8 alkene；The ethers is preferably selected from C4-C7 ethers, preferably
C4-C5 ethers.The ethers is for example including methyl tertiary butyl ether(MTBE) (MTBE), ethyl tert-butyl ether (ETBE) (MTBE), tert amyl methyl ether(TAME)
At least one of (TAME).
Preferably, olefin(e) centent 85-95wt%, preferably 90-95wt%.
Preferably, ethers content is 1-5wt%, preferably 3-5wt%.
Further preferred embodiment according to the present invention, the olefin-containing organic materials include 90-95wt%C8 alkene.
According to the preferred embodiment of the present invention, the olefin-containing organic materials further includes 3-5wt% methyl- tert fourths
Base ether.
In a preferred embodiment of the present invention, the olefin-containing organic materials is methyl tertiary butyl ether(MTBE) cracker
The heavy constituent material at weight-removing column bottom.The heavy constituent material includes 90-95wt%C8 alkene and 3-5wt% methyl tertiary butyl ether(MTBE)s.
In the present invention, the progress impregnation of SAPO-11 molecular sieves can aid in using olefin-containing organic materials and subtracts
Accessory substance generates in few reaction, especially most obvious in initial reaction stage effect.
According to the preferred embodiment of the present invention, the catalytic component b is described by the way that SAPO-11 molecular sieves are impregnated in
Certain time in olefin-containing organic materials, then dry, then roasted to prepare under an inert gas.
In the above-mentioned preparation process of catalytic component b, when the time of dipping is preferably 1.5-3.5 small, more preferably 2-3
Hour；
In the above-mentioned preparation process of catalytic component b, dry temperature is preferably 100-130 DEG C, and the dry time is excellent
Elect as 1.5-4 it is small when, more preferably 2.5-3.5 it is small when；
In the above-mentioned preparation process of catalytic component b, the temperature of roasting is preferably 250-350 DEG C, and the time of roasting is excellent
Elect as 1-3 it is small when.
According to the preferred embodiment of invention, in the catalytic component a, the metal of SAPO-11 molecular sieves is carried on
Element is selected from least one of group vib and VIII group metallic elements, is preferably selected from Ni, Co, Mo, Pd, Mn and Cr at least
It is a kind of.According to some preferred embodiments, the metallic element is selected from least one of Ni, Co and Mo.In preferable embodiment party
In formula, the catalytic component a can be loaded selected from foregoing bimetallic as active component.The present invention is using base metal member
Element is the active ingredient of catalytic component a, while reaction effect is improved, reduces production cost.
Preferably, in terms of the catalytic component a weight, the content of the metallic element is 10-20wt%, more preferably
12-18wt%, further preferred 15-18wt%.
The metal active constituent of the catalytic component a can be loaded by the way of incipient impregnation, exchange or blending
In on molecular sieve carrier.For example, it can be prepared by following steps：SAPO-11 molecules are impregnated with the aqueous solution of metal ion
Carrier is sieved, is then dried, is roasted；Alternatively, add in the acid solution used in the kneading and compacting of SAPO-11 molecular sieve preparation process
Enter metal ion, make the molecular sieve carried metal ions of SAPO-11, then dry, roast.The aqueous solution of the metal ion is institute
The aqueous solution of the water soluble salt of metallic element is selected, concentration is preferably 0.2-0.25g/ml.
In certain embodiments of the present invention, the preparation process of catalytic component a further includes the system of SAPO-11 molecular sieves
Standby step, the wherein preparation process of SAPO-11 molecular sieves can use conventional preparation process of the prior art.
According to the preferred embodiment of the present invention, the weight ratio of the catalytic component a and the catalytic component b are 5：
1-1：1, preferably 3：1–2：1.When the amount ratio of two kinds of catalytic components is in aforementioned range, preferable reactivity can be produced
Can, the butanes conversion and isobutene yield such as improved.
According to the present invention, the catalyst is the mixture of catalytic component a and catalytic component b, or the catalysis
Agent includes catalytic component a and catalytic component b independently.Catalyst provided by the invention when in use, can be to urge
The form of the mixture of agent component a and catalytic component b uses, but in a preferred embodiment, catalytic component a and urges
Agent component b is used separately without mixing, such as is loaded on respectively in the different beds of reactor, or same bed
In diverse location.According to the preferred embodiment of the present invention, the reaction raw materials containing butane are first main under the catalysis of catalytic component a
Generation dehydrogenation reaction, it is then further main under the catalysis of catalytic component b that isomerization reaction occurs, higher can be reached
Isobutene yield.
Catalysis butane production isobutene catalyst provided by the invention is particularly suitable in single-reactor by butane, especially
It is that normal butane changes into isobutene by a step process.In some embodiments, reaction raw materials can include fourth
The material of alkane, the especially material comprising normal butane, can be normal butane materials.
Present invention also offers application of the catalyst in isobutene production.
The method of butane production isobutene is catalyzed present invention also offers a kind of, including butane material will be contained and be passed through equipped with this
Reacted in the single-reactor of the invention catalyst, to generate isobutene.
According to the present invention, the single-reactor includes the first catalyst bed and the second catalyst bed.
According to the preferred embodiment of the present invention, catalytic component a and catalytic component b are loaded on the first catalyst respectively
Bed and the second catalyst bed.The material containing butane passes through the first catalyst bed and the second catalyst bed successively.That is,
In the preferred embodiment, catalytic component a and catalytic component b are packed into the form of mixed bed, and material containing butane first exists
The lower reaction of catalytic component a catalysis, then further reacts under the catalysis of catalytic component b, so carries out reaction process
Must be more abundant, so as to improve conversion ratio and selectivity.
" the first catalyst bed " and " the second catalyst bed " can be separately positioned on reactor upper and lower part.First
Catalyst bed and the second catalyst bed can among the inert medium of filling be boundary.
According to the preferred embodiment of the present invention, the reaction temperature of first catalyst bed is 450-550 DEG C, preferably
470-530℃。
According to the preferred embodiment of the present invention, the reaction temperature of second catalyst bed is 350-400 DEG C, preferably
360-390℃。
According to the preferred embodiment of the present invention, the reaction pressure of the first catalyst bed is 0-0.3MPa, is preferably
0.05-0.2MPa。
According to the preferred embodiment of the present invention, the reaction pressure of the second catalyst bed is 0-0.3MPa, is preferably
0.05-0.2MPa。
According to the preferred embodiment of the present invention, the feedstock quality air speed of the material containing butane is 2-5h-1, preferably 2.5-
4.0h-1。
In a preferred embodiment of the invention, by the way that catalytic component a and catalytic component b are loaded formation two respectively
A reaction zone, and two reaction zones are set into different reaction conditions to realize the butanes conversion of higher and isobutene choosing respectively
Selecting property, while the production of C8 accessory substances is reduced, make catalyst life.
In a preferred embodiment of the invention, it will contain after butane material is heated to 450-550 DEG C and be passed through the first catalysis again
Reacted in agent bed.
In a preferred embodiment of the invention, the reaction stream from the first catalyst bed is cooled to 350-400
It is passed through in the second catalyst bed and is reacted again after DEG C.
Before the reaction stream of each reaction zone enters reaction zone, the temperature of reaction stream is adjusted to corresponding reaction temperature
Spend in scope, be conducive to reaction mass and more fully reacted in each reaction zone.
Wherein, preferably described cooling between the first catalyst bed and the second catalyst bed by setting cooling dress
Put, the first catalyst bed reaction logistics is cooled to 350-400 DEG C before into the second catalyst bed to realize.Such as
The linkage section of first catalyst bed and the second catalyst bed adds cooling device, such as heat exchanger, make reaction stream from
After opening the first catalyst bed, into the reaction for being able to be cooled to the second catalyst bed reaction area before the second catalyst bed
Temperature range.
Alternatively, after by being cooled down by the first catalyst bed reaction logistics by conduit extraction reactor and by heat exchanger
Enter back into the second catalyst bed and reacted to realize.The embodiment has more preferable flexibility, from the first catalyst
The logistics of bed reaction zone outflow is more fully cooled down, and is controlled more easy.
Preferably, the distance between described first catalyst bed and the second catalyst bed are 0.5-0.8m.Especially exist
Set between first catalyst bed and the second catalyst bed in the embodiment of cooling device, which causes first
Catalyst bed reaction logistics is able to enough coolings before hypomere reaction zone is entered.The moderate spacing distance scope helps
Coordinate between two stage reaction is made with more preferably progress, so as to promote the raising of isobutene yield.
Preferably, separated between the catalytic component a and catalytic component b with inert material.The inert material
For this area conventional inert material, such as inert alumina ball.
According to the present invention, applicable reactor is preferably fixed bed reactors.
The catalyst or method provided according to the present invention, butanes conversion can reach more than 35.5%, such as 36-
42%；Isobutene conversion can reach more than 33%, such as 35-41%.Also, the present invention can advantageously obtain conversion of butane
Rate is more than 38%, while selective isobutene is more than 37%.
The catalysis butane production isobutene catalyst and method provided according to the present invention, improves butanes conversion and isobutyl
Alkene selectivity, reduces the production of C8 accessory substances, extends the service life of catalyst, and catalyst and isobutene are produced into
This relative moderate.The technique provided carries out in single reactor, is filled respectively especially by by catalytic component a and b
Different beds is filled in, and the reaction temperature of different bed reaction zones is set respectively, obtains excellent reaction effect.
Embodiment
The application is described further with reference to specific embodiment, it should be appreciated that the scope of the present invention is not limited to
This.
The material composition of reaction mass is measured by gas chromatography in following embodiments or comparative example, wherein, butane turns
Rate and selective isobutene are calculated by following calculation formula.
Embodiment 1
139.3g boehmites (are contained into 70wt%Al at room temperature2O3) stirred and be added to 800mL deionized waters
In, 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%) are then slowly added into, are stirred evenly, 45.9g Ludox is added and (contains
25wt%SiO2), 96.8g di-n-propyl amines and 426mL deionized waters are added afterwards, are again stirring for uniformly.By gained mixture
It is transferred in dynamic high-pressure reaction kettle, mixing speed is set to 350r/min, is warming up to 130 DEG C, when constant temperature aging 4 is small.Aging knot
Shu Hou, mixing speed are set to 140r/min, are warming up to 200 DEG C, when crystallization 36 is small at autogenous pressures.After the completion of crystallization, by crystalline substance
Change product filtering, washing, 120 DEG C of dryings, when 540 DEG C of roastings 6 are small, obtain SiO2/Al2O3Molar ratio=0.2, it is evengranular
SAPO-11 sieve samples, relative crystallinity 100%.
SAPO-11 molecular sieves and boehmite is dry-mixed, then be added dropwise aqueous solution of nitric acid be made can extrusion material, its
Middle SAPO-11 molecular sieves/boehmite weight ratio is 4:1.Mixed material is extruded into the bar of a diameter of 1.8mm, 120
It is DEG C dry 2 it is small when, when 540 DEG C of roastings 4 are small, molding SAPO-11 molecular sieves are made.
The above-mentioned SAPO-11 molecular sieves of 30g are weighed, and prepare the Ni (NO of the 0.55g/ml containing Ni3)2Solution, using isometric
When impregnation molecular sieve 2 is small, when then 120 DEG C of dryings 2 are small, when 540 DEG C of roastings 4 are small, Ni/SAPO-11 catalysis is made
Agent (catalytic component a).The load capacity of Ni is 17wt% in catalyst.
The above-mentioned SAPO-11 molecular sieves of 30g separately are weighed, with the restructuring at methyl tertiary butyl ether(MTBE) (MTBE) cracker weight-removing column bottom
When dividing (olefin-containing 91%, MTBE4.5%) immersion treatment 2 small, the then spare (catalysis when 120 DEG C of dryings 2 are small under nitrogen atmosphere
Agent component b).
In fixed bed reactors normal butane dehydrogenation-isomerization reaction is carried out by raw material of pure butane.Reactor epimere bed
The Ni/SAPO-11 catalyst of the layer filling above-mentioned preparations of 15g, hypomere bed load 15g as described above through organic materials immersion treatment
SAPO-11 molecular sieve catalysts, two kinds of catalyst are spaced apart at a distance of 0.5m with inert alumina ball.By butane reaction raw materials
500 DEG C are warming up to, then passes to the epimere bed reaction zone of reactor, mass space velocity 3.5h-1.Reaction carries out under normal pressure,
Epimere reaction temperature is 500 DEG C.Before hypomere bed reaction zone is entered, reaction stream is cooled to 350 DEG C, hypomere reaction temperature
For 350 DEG C.Catalyst reaction performance is shown in Table 1.
Embodiment 2
The shaping SAPO-11 molecular sieves of the preparation of 30g embodiments 1 are weighed, are impregnated in using equi-volume impregnating
In the cobalt sulfate solution of 0.60g/ml 3 it is small when, then at 110 DEG C it is dry 3 it is small when, roasted at 450 DEG C 3.5 it is small when, be made
Co/SAPO-11 catalyst (catalytic component a), 16wt% containing Co.
The above-mentioned SAPO-11 molecular sieves of 30g separately are weighed, with the restructuring at methyl tertiary butyl ether(MTBE) (MTBE) cracker weight-removing column bottom
When dividing (olefin-containing 91%, MTBE4.5%) immersion treatment 3 small, the then spare (catalysis when 120 DEG C of dryings 3 are small under nitrogen atmosphere
Agent component b).
In fixed bed reactors normal butane dehydrogenation-isomerization reaction is carried out by raw material of pure butane.Reactor epimere bed
The Co/SAPO-11 catalyst of the layer filling above-mentioned preparations of 15g, hypomere bed load 10g as described above through organic materials immersion treatment
SAPO-11 molecular sieve catalysts, two kinds of catalyst are spaced apart, and spacer is equipped with a distance of 0.6m with inert alumina ball
Cooling device.Butane reaction raw materials are warming up to 470 DEG C, then pass to reactor epimere bed reaction zone, mass space velocity is
2.5h-1.Reaction carries out under normal pressure, and epimere reaction temperature is 480 DEG C.Before hypomere reaction zone is entered, reaction stream is cooled down
To 370 DEG C, hypomere reaction temperature is 360 DEG C.Catalyst reaction performance is shown in Table 1.
Embodiment 3
The shaping SAPO-11 molecular sieves of the preparation of 30g embodiments 1 are weighed, 0.2g/ is impregnated in using equi-volume impregnating
In the nitric acid molybdenum solution of ml 3 it is small when, then at 130 DEG C it is dry 2 it is small when, roasted at 500 DEG C 3.5 it is small when, Mo/ is made
(load capacity of catalytic component a), Mo are 14wt% to SAPO-11 catalyst.
The above-mentioned SAPO-11 molecular sieves of 30g separately are weighed, with the restructuring at methyl tertiary butyl ether(MTBE) (MTBE) cracker weight-removing column bottom
It is then spare when 110 DEG C of dryings 4 are small under nitrogen atmosphere (to urge when dividing (olefin-containing 91%, MTBE4.5%) immersion treatment 2.5 small
Agent component b).
In fixed bed reactors normal butane dehydrogenation-isomerization reaction is carried out by raw material of pure butane.Reactor epimere bed
The Mo/SAPO-11 catalyst of the layer filling above-mentioned preparations of 10g, hypomere bed load 15g as described above through organic materials immersion treatment
SAPO-11 molecular sieve catalysts.Butane reaction raw materials are warming up to 500 DEG C, then pass to reactor epimere bed reaction zone,
Mass space velocity is 3.0h-1.Reaction carries out at 0.2 mpa, and epimere reaction temperature is 520 DEG C., will before hypomere reaction zone is entered
Reaction stream is cooled to 370 DEG C, and hypomere reaction temperature is 380 DEG C.Catalyst reaction performance is shown in Table 1.
Embodiment 4
With reference to embodiment 1, simply the reaction temperature of upper-lower section catalyst bed is 500 DEG C, remaining preparation condition and anti-
Answer condition constant, catalyst reaction performance is shown in Table 1.
Embodiment 5
With reference to embodiment 1, the load capacity of epimere Ni/SAPO-11 catalyst is 5wt%, remaining preparation condition and reaction bar
Part is constant, and catalyst reaction performance is shown in Table 1.
Comparative example 1
With reference to embodiment 1, simply hypomere bed catalyst is using without organic materials immersion treatment of the present invention
SAPO-11 molecular sieves, remaining preparation condition and reaction condition are constant, and catalyst reaction performance is shown in Table 1.
Comparative example 2
It is the Ni/SAPO-11 catalyst that upper-lower section catalyst bed loads the preparation of embodiment 1 with reference to embodiment 1,
Remaining preparation condition and reaction condition are constant, and catalyst reaction performance is shown in Table 1.
Comparative example 3
It is upper-lower section catalyst bed mixed packing with reference to embodiment 1, remaining preparation condition and reaction condition are constant,
Catalyst reaction performance is shown in Table 1.
1 normal butane dehydrogenation-isomerization catalyst performance of table
As the result of above example and comparative example (shown in table 1) as it can be seen that by selecting suitable catalytic component a and urging
Agent component b, and different catalysts bed select suitable reaction temperature, help to obtain the butanes conversion of raising at the same time
And selective isobutene, as shown in the comparison with embodiment 1-3 and the result of embodiment 4 and 5；Select suitable catalyst
Component a and catalytic component b, and two kinds of catalyst are reasonably combined also contributes to obtain good reactivity worth, as embodiment 1 with
Shown in the results contrast of comparative example 2,3.
In summary result of the test is as it can be seen that catalyst provided by the invention and the method with its catalysis butane for isobutene
Bring the raising of obvious reactivity worth.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of the invention recorded, different embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In above-mentioned each embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, this is by by this area skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only exemplary mode, not purport
In the limitation present invention.
Claims (11)
1. a kind of catalyst for being catalyzed butane production isobutene, including catalytic component a and catalytic component b, the catalyst
Component a is the SAPO-11 molecular sieves of carried metal element, and the catalytic component b is to be impregnated simultaneously by olefin-containing organic materials
Dried SAPO-11 molecular sieves.
2. catalyst according to claim 1, it is characterised in that the olefin-containing organic materials includes C7-C12 alkene
And/or C4-C7 ethers；Preferably, the olefin-containing organic materials includes 85-95wt%, preferably 90-95wt%C7-C12 alkene
And/or 3-5wt%C4-C7 ethers；It is highly preferred that the olefin-containing organic materials includes 90-95wt%C8 alkene and/or 3-
5wt% methyl tertiary butyl ether(MTBE)s；More preferably described olefin-containing organic materials is the weight at methyl tertiary butyl ether(MTBE) cracker weight-removing column bottom
Component materials.
3. catalyst according to claim 1 or 2, it is characterised in that the catalytic component b passes through SAPO-11 points
Son sieve is impregnated in certain time in the olefin-containing organic materials, then dries under an inert gas, then roasted to prepare；
When the time of the dipping is preferably 1.5-3.5 small, the temperature of the drying is preferably 100-130 DEG C, and the dry time is preferred
For 1.5-4 it is small when, the temperature of roasting is preferably 250-350 DEG C, when the time of roasting is preferably 1-3 small.
4. catalyst according to any one of claim 1-3, it is characterised in that described in the catalytic component a
Metallic element is selected from least one of group vib and VIII group metallic elements, is preferably selected from Ni, Co, Mo, Pd, Mn and Cr
It is at least one；Preferably, in terms of the catalytic component a weight, the content of the metallic element is 10-20wt%, more preferably
12-18wt%.
5. according to the catalyst any one of claim 1-4, it is characterised in that the catalytic component a and described urge
The weight ratio of agent component b is 5:1-1:1, it is preferably 3:1-2:1.
6. application of the catalyst in isobutene production according to any one of claim 1-5.
7. the method for butane production isobutene is catalyzed a kind of, including butane material will be contained and be passed through equipped with according in claim 1-5
Reacted in the single-reactor of any one of them catalyst, to generate isobutene.
8. the method according to the description of claim 7 is characterized in that the single-reactor include the first catalyst bed and
Second catalyst bed, catalytic component a are seated in the first catalyst bed, and catalytic component b is loaded on the second catalyst bed
Layer, the material containing butane pass through the first catalyst bed and the second catalyst bed successively.
9. according to the method described in claim 8, it is characterized in that, the reaction temperature of first catalyst bed is 450-
550 DEG C, preferably 470-530 DEG C；And/or the reaction temperature of second catalyst bed is 350-400 DEG C, preferably 360-390
℃；It is preferred that the reaction pressure of the first catalyst bed and the second catalyst bed is 0-0.3MPa, it is preferably 0.05-
0.2MPa；It is preferred that the feedstock quality air speed of the material containing butane is 2-5h-1。
10. method according to claim 8 or claim 9, it is characterised in that will contain after butane material is heated to 450-550 DEG C again
It is passed through in the first catalyst bed and is reacted；And/or the reaction stream from the first catalyst bed is cooled to 350-
It is passed through in the second catalyst bed and is reacted again after 400 DEG C.
11. according to the method described in claim 10, it is characterized in that, the cooling is by the first catalyst bed and second
Cooling device is set between catalyst bed, the first catalyst bed reaction logistics is cooled down before entering the second catalyst bed
Realized to 350-400 DEG C, or by the way that by conduit the first catalyst bed reaction logistics is drawn reactor and by changing
Enter back into the second catalyst bed and reacted to realize after hot device cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610956172.5A CN108014845B (en) | 2016-11-03 | 2016-11-03 | Catalyst for producing isobutene by catalyzing butane and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610956172.5A CN108014845B (en) | 2016-11-03 | 2016-11-03 | Catalyst for producing isobutene by catalyzing butane and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108014845A true CN108014845A (en) | 2018-05-11 |
| CN108014845B CN108014845B (en) | 2020-11-10 |
Family
ID=62083897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610956172.5A Active CN108014845B (en) | 2016-11-03 | 2016-11-03 | Catalyst for producing isobutene by catalyzing butane and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108014845B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117101714A (en) * | 2023-07-30 | 2023-11-24 | 南京工业大学 | Magnesium modified NiAPO-11 molecular sieve catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175048B1 (en) * | 1998-12-11 | 2001-01-16 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and processes therefor and therewith |
| AU2002316130A1 (en) * | 2001-07-12 | 2003-01-29 | Exxonmobil Chemical Patents Inc. | Producing maleic anhydride from a c4 stream in an oxygenate to olefin process |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
| CN104174433A (en) * | 2013-05-23 | 2014-12-03 | 中国石油化工股份有限公司 | An n-butylene isomerization catalyst and a preparing method thereof |
| CN104557396A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of n-butene |
-
2016
- 2016-11-03 CN CN201610956172.5A patent/CN108014845B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175048B1 (en) * | 1998-12-11 | 2001-01-16 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and processes therefor and therewith |
| AU2002316130A1 (en) * | 2001-07-12 | 2003-01-29 | Exxonmobil Chemical Patents Inc. | Producing maleic anhydride from a c4 stream in an oxygenate to olefin process |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
| CN104174433A (en) * | 2013-05-23 | 2014-12-03 | 中国石油化工股份有限公司 | An n-butylene isomerization catalyst and a preparing method thereof |
| CN104557396A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of n-butene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117101714A (en) * | 2023-07-30 | 2023-11-24 | 南京工业大学 | Magnesium modified NiAPO-11 molecular sieve catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108014845B (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3317236B1 (en) | Methods for producing propylene | |
| JP5562345B2 (en) | Olefin oligomerization | |
| CN101679146B (en) | Propylene production | |
| CN104549480B (en) | Composite molecular sieve catalysts of binder free SAPO 34/ZSM 5 and its production and use | |
| CN104549479B (en) | Catalyst for preparing aromatics by use of methanol and preparation method of catalyst | |
| CN102266793A (en) | Catalyst for producing propylene and producing method and application thereof | |
| CN102933527B (en) | Process for co-oligomerization of olefins | |
| JP2019501767A (en) | Palladium-based supported hydrogenation catalyst, production method thereof, and use thereof | |
| KR20130046458A (en) | A method for preparing 1,3-butadiene using continuous reactors | |
| CN101734987A (en) | Method for preparing ethylene and propylene from C4 hydrocarbons | |
| JP2009179801A (en) | Method for producing liquefied petroleum gas | |
| CN104549483B (en) | Composite molecular screens of binder free SAPO 34/ZSM 5 and preparation method thereof | |
| EA024895B1 (en) | Catalyst for preparing ethylene and propylene from methanol and/or dimethyl ether, preparation and use thereof | |
| CN107107041A (en) | Metathesis catalyst and its application method on the metal oxide Zeolite support of mixing | |
| CN103785482B (en) | A kind of deactivating process for the treatment of of olefin isomerization catalyst | |
| CN108014845A (en) | A kind of catalyst for being catalyzed butane production isobutene and its application | |
| CN102060647B (en) | Selective hydrogenation method for carbon-dioxide fraction | |
| CN104109071B (en) | The method of cracked C 5 fraction propylene | |
| US10384993B2 (en) | Method for producing hydrocarbons and alcohols | |
| CN115888797B (en) | Catalyst for preparing ethylene and propylene by cracking carbon five-carbon hexaalkane and preparation method and application thereof | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN113582801B (en) | Process for preparing isooctenes by mixing carbon four selective overlapping | |
| CN106466637A (en) | Binderless ZSM-5-11/SAPO-34 composite molecular sieve catalyst and preparation method thereof | |
| JP6366407B2 (en) | Oxidative dehydrogenation catalyst, method for producing oxidative dehydrogenation catalyst, and oxidative dehydrogenation method | |
| US20230348341A1 (en) | Process for converting olefins to distillate fuels |
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 |