CN106582603A - Preparation and application of alumina catalyst for dehydration reactions of isobutanol - Google Patents
Preparation and application of alumina catalyst for dehydration reactions of isobutanol Download PDFInfo
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- CN106582603A CN106582603A CN201510684206.5A CN201510684206A CN106582603A CN 106582603 A CN106582603 A CN 106582603A CN 201510684206 A CN201510684206 A CN 201510684206A CN 106582603 A CN106582603 A CN 106582603A
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- dehydration
- isobutanol
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- catalyst
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 59
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 30
- 230000032683 aging Effects 0.000 claims abstract description 24
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 12
- 239000003518 caustics Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims description 56
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 19
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 33
- 238000007598 dipping method Methods 0.000 abstract description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 2
- 206010013786 Dry skin Diseases 0.000 description 21
- 239000004411 aluminium Substances 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000428 dust Substances 0.000 description 11
- 238000007493 shaping process Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000004575 stone Substances 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 isobutyl alkene Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 230000001568 sexual effect Effects 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a modified alumina catalyst for the dehydration reactions of isobutanol. The preparation method comprises the following steps: (a) mixing an aluminum salt solution and an alkali solution; (b) subjecting the mixture obtained in the step (a) to an aging treatment to obtain pseudo-boehmite gel; (c) mixing the pseudo-boehmite gel obtained in the step (b) with amorphous silica-alumina, drying the mixture, and carrying out extrusion moulding to obtain a carrier; and (d) dipping the carrier obtained in the step (c) in a caustic alkali solution and a calcium salt solution, and performing drying and burning to obtain the modified alumina catalyst. The prepared catalyst is applied to dehydration reactions of isobutanol to prepare isobutene; and the conversion rate of isobutanol and selectivity of isobutene are both improved.
Description
Technical field
The present invention relates to a kind of preparation method of aluminium oxide catalyst, more particularly to a kind of to be used for isobutyl dehydration of alcohols
The preparation method of the aluminium oxide catalyst of reaction.The invention further relates to a kind of isobutyl dehydration of alcohols prepares the side of isobutene
Method.
Background technology
Isobutene is a kind of important fine chemical material, is also the important monomer of synthetic rubber and resin.MTBE
(methyl tertiary butyl ether(MTBE)) cracking is to produce the topmost method of isobutene at present, right with abundant raw material source
Equipment and material requirements are low, the little advantage of environmental pollution.
But, the increasingly elevated price of crude oil has promoted people to find the production method of petroleum replacing chemical industry, its
Middle isobutyl dehydration of alcohols increasingly causes concern.The source of isobutanol can be from addition to the conventional methods such as carbonylation synthesis, also
Coal Chemical Industry Route is produced, i.e., by synthesis gas (CO, H2And CO2Mixture) by similar to Fischer-Tropsch
(Fischer-Tropsch) the method production of synthesis, obtains the mixture of higher alcohol, wherein about 30% accessory substance is
Isobutanol.There is the advantage on reserves due to coal, this technique has greatly enriched the source of isobutanol.In addition it is near
Nian Lai, biomass isobutanol technology is developed rapidly, and has been developed over micro-organisms long-chain alcohol
Method, becomes the another source of isobutene, has the advantages that raw material is renewable, environmentally friendly.Isobutanol dehydration
Production isobutene, the catalyst for being used mainly has a few classes of molecular sieve, aluminum oxide and modified aluminas, wherein oxygen
Change aluminium-based catalyst activity relatively low, but selective isobutene is higher than molecular sieve.With the improvement of existing catalyst,
The conversion ratio of isobutanol dehydration brings up to more than 99.5%, but is limited to the selectivity of catalyst and is difficult to improve,
The purity of product isobutene fails to reach chemical grade standard at present.
The A of Chinese patent CN 102892729 disclose a kind of isobutanol and are dehydrated simultaneously and skeletal isomerization production alkene
The method of hydrocarbon, used catalyst is the modified aluminum oxide such as Si-Al molecular sieve, sial phosphorus molecular sieve and titanium, fluorine,
And provide using the dehydration results of aluminium oxide catalyst in comparative example.Wherein the catalysis activity of molecular sieve compared with
Height, in 350 DEG C of reaction temperature, reaction pressure 2bar, liquid feed air speed 7-21h-1Under conditions of, isobutanol
Conversion ratio is more than 99.5%, selective isobutene 41-43%；Using the gama-alumina of Sasol productions as catalysis
Reaction temperature need to be improved to 380 DEG C during agent, but selective isobutene is higher, up to 90-94%.
Separately there is document to describe isobutanol to be reacted with very low Feed space velocities under aluminium oxide catalyst effect
(Zhang Lili, Gao Junbin, Yao Zhilong. the research of biological isobutyl dehydration of alcohols preparing isobutene catalyst, fine oil
Work [J] .2013,30 (2)：17-20), it is different under conditions of reaction pressure 0.1MPa in 270 DEG C of reaction temperature
Butanol conversion ratio and selective isobutene are respectively 99.46% and 98.76%.
In the presence of existing aluminium oxide catalyst, isobutanol dehydration production isobutene is unable to reach chemical grade
The index of isobutene, can only be used as the raw material of MTBE synthesizers, and it need to be via MTBE synthesis-cracking
Process, is just obtained chemical grade isobutene, and production cost is higher.
The content of the invention
In view of above the deficiencies in the prior art, a kind of preparation method of modified alumina catalyst of present invention proposition,
This catalyst is applied to into isobutanol dehydration, the production isobutene choosing of isobutanol dehydration can be effectively overcome
The relatively low technical problem of selecting property.
Present invention also offers a kind of method that isobutyl dehydration of alcohols prepares isobutene, the high isobutanol of the method acquisition
Conversion ratio, while also obtaining high selective isobutene.
The invention provides a kind of preparation method of the modified alumina catalyst for isobutanol dehydration, institute
The method of stating is comprised the following steps：
A) aluminum salt solution and alkali lye are mixed；
B) mixture for obtaining step a) carries out burin-in process, obtains boehmite gel；
C) the boehmite gel for obtaining step b) mixes with amorphous silica-alumina, is dried, extrusion molding,
Prepared carrier；
D) the carrier impregnation aqueous caustic for obtaining step c) and calcium salt soln, then dry, roasting.
Composite molding and the alkali lye, calcium salt soln of the present invention by aluminium oxide catalyst with amorphous silica-alumina
With the load of aqueous caustic, the quantity and intensity of catalyst surface strong acid center are changed, reduce various alkene
Interconversion reaction, so as to reduce dehydration in isobutyl alkene isomer generation, generate more isobutenes, effectively
Improve selectivity and the activity of catalyst.
According to the present invention, in step a), the aluminium salt is preferably selected from aluminum nitrate, aluminium chloride and aluminum sulfate
At least one.Preferably, the concentration of the aluminum salt solution is 0.05-0.5mol/L, preferred 0.1-0.2mol/L.
According to the present invention, in step a), the alkali lye is preferably selected from ammoniacal liquor, NaOH, potassium hydroxide, hydrogen
At least one in calcium oxide and barium hydroxide solution.Preferably, the concentration of the alkali lye is 0.2-1.0mol/L,
It is preferred that 0.4-0.6mol/L.Or, the volumetric concentration of the ammoniacal liquor is preferably 1-10%, more preferably 3-6%.
Preferably, in step a), the mixing is carried out by titration, and titration temperature is 30-80 DEG C, preferably
45-65℃；Titration end-point pH value is 8-9, preferred 8.5-9；Incorporation time be 1-4 hours, preferred 1.5-3
Hour.
Preferably, in step b), aging temperature is 65-95 DEG C, preferred 75-90 DEG C；Ageing time is 10-24
Hour.
As known to the skilled person, amorphous silica-alumina generally can be by using silicate and the common glue side of aluminium salt
Method is prepared.The amorphous silica-alumina for using in the present invention is amorphous silicon as above commonly used in the art
Aluminium.
According to the present invention, in step c), counted as 100 parts by weight with the boehmite gel, institute
Amorphous silica-alumina consumption is stated for 1～10 parts by weight, preferably 2～6 parts by weight.Or, in the carrier
Middle amorphous silica-alumina mass content is preferably 1-9%, more preferably 2-5%.In the present invention, will be without fixed
Shape sial is added in aluminium oxide catalyst, especially in the range of usage amount as above, can improve aluminum oxide
The specific surface area and surface acidity of catalyst, is more beneficial for combining for subsequent solid alkali center and catalyst.According to pushing away
Survey, this may be derived from higher acidity and the larger specific surface area that amorphous silica-alumina has.
In preferred embodiments, the carrier that the step c) is obtained can be further dried, roasting, wherein
Baking temperature is 90-150 DEG C, preferred 100-120 DEG C.
In preferred embodiments, in step c), after boehmite gel mixes with amorphous silica-alumina
Re-dry after filtering.
According to the present invention, in the step d), the aqueous caustic is preferably selected from potassium hydroxide and/or hydroxide
Sodium solution.
Preferably, the aqueous caustic concentration be 0.1-5mol/L, also preferably 1-3mol/L, further preferably
For 1.5-2.5mol/L.Or, the mass concentration of the aqueous caustic is preferably 5-20%, more preferably
10-15%.
In the present invention, in step d), the sequencing of the aqueous caustic and calcium salt soln dipping is without spy
Do not limit, such as can first impregnated in aqueous caustic and impregnated in calcium salt soln again, it is also possible to first impregnated in calcium salt molten
Impregnated in aqueous caustic solution in liquid again.
According to the present invention, the calcium salt is preferably selected from least one in calcium nitrate, calcium sulfate and calcium chloride.
Preferably, the concentration of the calcium salt soln be 0.1-3mol/L, preferably 0.2-1.0mol/L, preferably
0.3-0.6mol/L.Or, the mass concentration of the calcium salt soln is preferably 1-20%, more preferably 5-10%.
In preferred embodiments, in step d), the baking temperature is 90-150 DEG C, preferably
100-120℃；Sintering temperature is 300-600 DEG C, preferred 400-500 DEG C.
Present invention also offers a kind of modified alumina catalyst for obtaining prepared according to the methods of the invention, it compares table
Area is 180-240m2/ g, pore volume is 0.3-0.7ml/g.As can be seen here, the aluminium oxide catalyst that the present invention is provided
More solid base centers can be loaded, more improves catalyst surface acidity, be kept more in dehydration
Good catalytic stability, realizes higher catalysis Selection effect.
Further, present invention also offers a kind of isobutyl dehydration of alcohols method for preparing isobutene, including making isobutyl
Alcohol carries out being dehydrated instead in the presence of the modified alumina catalyst that the method provided according to the present invention is prepared
Should, obtain isobutyl ene product.
In a specific embodiment, the method that the isobutyl dehydration of alcohols prepares isobutene is included according to the present invention
Method as defined above prepare modified alumina catalyst, in being placed on dehydration reactor, then by isobutanol
In being passed through the dehydration reactor, dehydration is carried out under dehydration conditions.
Wherein, dehydration conditions include：Dehydration temperature is 260-330 DEG C, preferred 280-310 DEG C；Dehydration is anti-
Pressure is answered to be 0.1-0.5MPa, preferred 0.2-0.3MPa；Isobutanol Feed space velocities 0.5-1h-1, preferred 0.6-0.7h-1。
Isobutyl dehydration of alcohols is implemented according to the method that the present invention is provided and prepares isobutene reaction, isobutyl alcohol conversion can reach
To 99.5%, selective isobutene can reach 99.3%.This is a kind of significant effect for industrial production
Lifted.
In a preferred embodiment, the method that the isobutyl dehydration of alcohols prepares isobutene is included in reaction and starts
When, water is passed through in dehydration reactor, and stop water inlet when isobutyl alcohol conversion is reduced to setting value.According to
The present invention, the setting value is preferably 96-98.8%, further preferred 97.5-98.3%.
As known to the skilled person, by the way that detection is into the isobutanol of reactor and leaves the different of reactor
The content of butanol, would know that the conversion ratio of isobutanol.In the present invention, the change of the amount of isobutanol and isobutene
Situation by online analytical instrument monitor in real time, or can be monitored by artificial timing sampling measure.Need
Illustrate, the normal time of the amount and then acquisition conversion ratio that determine isobutanol by manual sampling can't be to entering
The control effect of water produces substantial effect.
Count by 100 parts by weight of the isobutanol, the water consumption be 5-20 parts by weight, preferably 10-15
Parts by weight.By the method, the selectivity of isobutene can reach more than 99.4%.
In prior art, the water generated in bed blending reaction can reduce in dehydration isobutyl alcohol conversion and different
The selectivity of butylene, it is necessary to remove the water in raw material in advance and remove product water in time during reaction.
However, the present inventor in experiments it is found that, catalyst of the present invention used in isobutanol dehydration
When, add appropriate water to be conducive to the carrying out reacted on the contrary in initial reaction stage, obtain preferable conversion ratio and selection
Sexual balance.
In the present invention, the dehydration reactor can be fixed bed reactors or moving-burden bed reactor.Due to root
The catalyst prepared according to the present invention possesses good stability, therefore dehydration can be in two parallel connections
Continuously carry out in reactor, wherein when a reactor runs, another reactor carries out catalyst regeneration.
The catalyst of the present invention can also regenerate.
The product that dehydration is obtained is separated it is possible to further pass through conventional method, to remove isobutyl
Alcohol and carbon five, and then the isobutene that purity is 99.4% is obtained.
Prepare catalyst of the present invention used in isobutene reaction in isobutyl dehydration of alcohols, can save from raw material and
The equipment and technique of eliminating water, substantially reduces production cost in production.
The invention provides a kind of preparation method of modified alumina catalyst, will be catalyzed according to obtained in the method
Agent is used in isobutanol dehydration production isobutene, on the basis of isobutyl alcohol conversion 99.5%, isobutene
Performance is selected to reach 99.3%, eliminating in prior art must pass through crude product to reach chemical grade isobutene
The process of MTBE synthesis-cracking, realizes the efficient, effect of production energy-saving chemical grade isobutene.
Specific embodiment
Although the present invention is described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side, difference that the present invention is recorded
The each several part of specific embodiment and the various features enumerated can be combined or all or part of exchange.Above-mentioned
Each specific embodiment in, those with reference to another embodiment embodiment can suitably with its
Its embodiment combination, this is will be to understand by those skilled in the art.Additionally, those skilled in the art
It will be understood that, description above is only the mode of example, it is no intended to limit the present invention.
Embodiment 1
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.6g amorphous silicons aluminium powder and add appropriate above-mentioned gel (amorphous silica-alumina weight:Intend thin water aluminium
Stone gel weight=6:100) in, stir 1 hour at room temperature, with after 5% dust technology mixing after filtering drying
Into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4 are little
When after be prepared into carrier.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
290 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 2
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.4g amorphous silicons aluminium powder and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin water
Aluminium stone gel weight=4:100) in, stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Afterwards into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
302 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 3
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.6g amorphous silicons aluminium powder and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin water
Aluminium stone gel weight=6:100) in, stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Afterwards into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 16% (2.8mol/L) impregnates above-mentioned carrier 1 hour, then prepares
Ca (the NO of 10% (0.6mol/L)3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3
Hour, 500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
302 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 4
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.4g amorphous silicons aluminium powder and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin water
Aluminium stone gel weight=4:100) in, stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Afterwards into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
320 DEG C, reaction pressure 0.1MPa, Feed space velocities 1.0h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 5
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 45 DEG C of 500ml, 0.5mol/L is added dropwise
Ca(OH)2Solution continues stirring 2 hours, then hydrothermal aging 24 hours at 70 DEG C to pH=8.It is aging
The gel of generation is cooled to after end standby after room temperature.
Weigh 1.0g amorphous silicons aluminium powder and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin water
Aluminium stone gel weight=10:100) in, stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Into column type, body diameter is 2mm to extrusion after conjunction.100 DEG C of Jing dryings 3 hours after shaping, 400 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 6% (1mol/L) impregnates above-mentioned carrier 1 hour, then prepares 6%
(0.4mol/L) CaSO4Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
400 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
302 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 6
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 65 DEG C of 500ml, 0.8mol/L is added dropwise
Ca(OH)2Solution continues stirring 2 hours, then hydrothermal aging 24 hours at 85 DEG C to pH=8.5.Always
Change is cooled to the gel of generation after terminating standby after room temperature.
Weigh 1.0g amorphous silicons aluminium powder and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin water
Aluminium stone gel weight=10:100) in, stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Into column type, body diameter is 2mm to extrusion after conjunction.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 18% (3mol/L) impregnates above-mentioned carrier 1 hour, then prepares 16%
(1mol/L) CaCl2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours, 500 DEG C
Roasting is prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
302 DEG C, reaction pressure 0.2MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result are shown in
Table 1.
Embodiment 7
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 75 DEG C of 500ml, 0.3mol/L is added dropwise
Ca(OH)2Solution continues stirring 2 hours, then hydrothermal aging 24 hours at 95 DEG C to pH=9.It is aging
The gel of generation is cooled to after end standby after room temperature.
Weigh amorphous silicon aluminium powder in 0.2g and add (amorphous silica-alumina weight in appropriate above-mentioned gel:Intend thin
Diaspore gel weight=2:100), stir 1 hour at room temperature, mixed with 5% dust technology after filtering drying
Afterwards into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 600 DEG C of roastings 4
Carrier is prepared into after hour.
The KOH solution for preparing 20ml 18% (3mol/L) impregnates above-mentioned carrier 1 hour, then prepares 16%
(1mol/L) CaCl2Solution 20ml impregnates above-mentioned carrier 2 hours, in 150 DEG C of dryings 3 hours, 600 DEG C
Roasting is prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
320 DEG C, reaction pressure 0.2MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result
It is shown in Table 1.
Embodiment 8
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.6g amorphous silicons aluminium powder and add appropriate above-mentioned gel (amorphous silica-alumina weight:Intend thin water aluminium
Stone gel weight=6:100) in, stir 1 hour at room temperature, with after 5% dust technology mixing after filtering drying
Into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4 are little
When after be prepared into carrier.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
290 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1, water flowing (the water weight when reaction starts:Isobutanol
Weight=8:100), and detecting stop when isobutyl alcohol conversion is down to below 98.5% water inlet.Isobutanol turns
Rate and selective isobutene the results are shown in Table 1.
Embodiment 9
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
The gel of generation is cooled to after beam standby after room temperature.
Weigh 0.6g amorphous silicons aluminium powder and add appropriate above-mentioned gel (amorphous silica-alumina weight:Intend thin water aluminium
Stone gel weight=6:100) in, stir 1 hour at room temperature, with after 5% dust technology mixing after filtering drying
Into column type, body diameter is 2mm to extrusion.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings 4 are little
When after be prepared into carrier.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
290 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1, water flowing (the water weight when reaction starts:Isobutanol
Weight=16:100), and detecting stop when isobutyl alcohol conversion is down to below 97.8% water inlet.Isobutanol turns
Rate and selective isobutene the results are shown in Table 1.
Comparative example 1
Weigh 37.51g (0.1mol) aluminum nitrate to be dissolved in the hot water of 55 DEG C of 500ml, 0.6mol/L ammonia is added dropwise
The aqueous solution continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C to pH=8.5.Aging knot
Beam Jing is filtered, washing, and, into column type, body diameter is 2mm to concoct simultaneously extrusion with 5% dust technology after drying.
100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
325 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result are shown in
Table 1.
Comparative example 2
50g amorphous silica-aluminas are weighed, with extrusion after 5% dust technology blending into column type, body diameter is
2mm.100 DEG C of Jing dryings 3 hours after shaping, 500 DEG C of roastings are prepared into carrier after 4 hours.
The KOH solution for preparing 100ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8%
(0.5mol/L) Ca (NO3)2Solution 100ml impregnates above-mentioned carrier 2 hours, in 120 DEG C of dryings 3 hours,
500 DEG C of roastings are prepared into catalyst after 4 hours.
Carry out isobutanol dehydration on fixed bde catalyst, loaded catalyst is 30ml, reaction temperature
261 DEG C, reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene result are shown in
Table 1.
Table 1
Above example and comparative example illustrate that the catalyst prepared using the method for the invention is turned in isobutanol
Under conditions of rate 99.5%, selective isobutene is up to 99.3%.Further, suitably add in the reaction
Enter water, can be in the case where the not clear aobvious decline of isobutyl alcohol conversion be ensured, the selectivity for making isobutene is carried
Height, for example, reach 99.4% or more.It is different that the present invention can be directly produced chemical grade by isobutanol dewatering process
Butylene, so as to eliminate the process through MTBE synthesis-cracking, greatly reduces the life of chemical grade isobutene
Produce cost.
Claims (11)
1. a kind of preparation method of the modified alumina catalyst for isobutanol dehydration, methods described includes
Following steps：
A) aluminum salt solution and alkali lye are mixed；
B) mixture for obtaining step a) carries out burin-in process, obtains boehmite gel；
C) the boehmite gel for obtaining step b) mixes with amorphous silica-alumina, is dried, extrusion molding,
Prepared carrier；
D) the carrier impregnation aqueous caustic for obtaining step c) and calcium salt soln, then dry, roasting.
2. method according to claim 1, it is characterised in that in step a), the mixing passes through
Titration is carried out, and titration temperature is 30-80 DEG C, preferred 45-65 DEG C；Titration end-point pH value is 8-9, preferred 8.5-9；
Incorporation time be 1-4 hours, preferred 1.5-3 hours；And/or
In step b), aging temperature is 65-95 DEG C, preferred 75-90 DEG C；Ageing time is 10-24 hours.
3. method according to claim 1 and 2, it is characterised in that the concentration of the aluminum salt solution is
0.05-0.5mol/L, preferred 0.1-0.2mol/L；It is preferred that the aluminium salt is in aluminum nitrate, aluminium chloride and aluminum sulfate
At least one；The concentration of the alkali lye is 0.2-1.0mol/L, preferred 0.4-0.6mol/L；It is preferred that the alkali lye
At least one in ammoniacal liquor, NaOH, potassium hydroxide, calcium hydroxide and barium hydroxide solution.
4. the method according to any one of claim 1-3, it is characterised in that in step c), with
The boehmite gel is 100 parts by weight meters, and the amorphous silica-alumina consumption is 1～10 parts by weight,
Preferably 2～6 parts by weight.
5. the method according to any one of claim 1-4, it is characterised in that in step d), institute
Aqueous caustic concentration is stated for 0.1-5mol/L, preferably 1.5-2.5mol/L；It is preferred that the aqueous caustic is selected from hydrogen-oxygen
Change potassium and/or sodium hydroxide solution；The concentration of the calcium salt soln is 0.1-3mol/L, preferred 0.3-0.6mol/L；
It is preferred that at least one of the calcium salt in calcium nitrate, calcium sulfate and calcium chloride；It is preferred that sintering temperature is
300-600 DEG C, preferred 400-500 DEG C.
6. the modified aluminas catalysis that a kind of method according to any one in claim 1-5 is prepared
Agent, its specific surface area is 180-240m2/ g, pore volume is 0.3-0.7ml/g.
7. a kind of method that isobutyl dehydration of alcohols prepares isobutene, including making isobutanol according in claim 1-5
Dehydration is carried out in the presence of the modified alumina catalyst that method described in any one is prepared, is obtained
Isobutyl ene product.
8. method according to claim 7, it is characterised in that methods described includes：According to claim
Method in 1-5 described in any one prepares modified alumina catalyst, in being placed on dehydration reactor, so
Isobutanol is passed through in the dehydration reactor afterwards, dehydration is carried out under dehydration conditions, obtain isobutene product
Thing.
9. method according to claim 8, it is characterised in that the dehydration conditions include：Dehydration
Temperature be 260-330 DEG C, preferred 280-310 DEG C；And/or the pressure of dehydration is 0.1-0.5MPa, preferably
0.2-0.3MPa；And/or isobutanol Feed space velocities 0.5-1h-1, preferred 0.6-0.7h-1。
10. method according to claim 8 or claim 9, it is characterised in that when reaction starts, water is led to
In entering dehydration reactor, and stop water inlet, the preferably setting value when isobutyl alcohol conversion is reduced to setting value
For 96-98.8%, further preferred 97.5-98.3%.
11. methods according to claim 10, it is characterised in that with the isobutanol as 100 weight portions
Number meter, the water consumption be 5～20 parts by weight, preferably 10～15 parts by weight.
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| CN113926475A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Dehydration catalyst, preparation method and application thereof in production of isobutene through dehydration of tertiary butanol |
| WO2024235790A1 (en) | 2023-05-12 | 2024-11-21 | Basf Se | Mixed guerbet reaction of ethanol and methanol to produce isobutanol |
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| CN107118069A (en) * | 2017-06-17 | 2017-09-01 | 安徽海德石油化工有限公司 | A kind of method that utilization isobutyl dehydration of alcohols prepares isobutene |
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| WO2021200689A1 (en) * | 2020-03-31 | 2021-10-07 | 三菱ケミカル株式会社 | Catalyst, method for producing isobutylene, method for producing methacrylic acid, and method for producing methyl methacrylate |
| CN113926475A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Dehydration catalyst, preparation method and application thereof in production of isobutene through dehydration of tertiary butanol |
| CN113926475B (en) * | 2020-06-29 | 2024-01-26 | 中国石油化工股份有限公司 | Dehydration catalyst, preparation method and application thereof in tert-butyl alcohol dehydration to produce isobutene |
| WO2024235790A1 (en) | 2023-05-12 | 2024-11-21 | Basf Se | Mixed guerbet reaction of ethanol and methanol to produce isobutanol |
| WO2024235791A1 (en) | 2023-05-12 | 2024-11-21 | Basf Se | Process for the preparation of polyisobutene from olefins from isobutanol obtained from mixed guerbet reaction of ethanol and methanol |
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