CN109232196A - A kind of preparation method of methyl tertiary butyl ether(MTBE) - Google Patents
A kind of preparation method of methyl tertiary butyl ether(MTBE) Download PDFInfo
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- CN109232196A CN109232196A CN201811276815.7A CN201811276815A CN109232196A CN 109232196 A CN109232196 A CN 109232196A CN 201811276815 A CN201811276815 A CN 201811276815A CN 109232196 A CN109232196 A CN 109232196A
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- mtbe
- butyl ether
- tertiary butyl
- methyl tertiary
- preparation
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 20
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000020477 pH reduction Effects 0.000 claims abstract description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 241001122767 Theaceae Species 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 7
- 235000013824 polyphenols Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 238000007373 indentation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- -1 acetum Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic 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 invention discloses a kind of preparation methods of methyl tertiary butyl ether(MTBE), are related to chemical technology field.The present invention is using montmorillonite as carrier, by acidification, metatitanic acid is ester modified, nano-titanium dioxide load and etc. catalyst is made, the activity and stability of the catalyst are higher than the styrene-divinylbenzene copolymer that uses of the prior art for the sulfonate resin of matrix, it can be recycled after catalyst regeneration simultaneously, obtained stable product quality, selectivity is good, is suitable for industrialized production.
Description
Technical field:
The present invention relates to chemical technology fields, and in particular to a kind of preparation method of methyl tertiary butyl ether(MTBE).
Background technique:
Methyl tertiary butyl ether(MTBE) is also known as 2- methoxyl group -2- methylpropane, the entitled tert-butyl methyl ether of English,
Abbreviation MTBE, is a kind of important industrial chemicals, and methyl tertiary butyl ether(MTBE) available perform an analysis solvent, extractant can be prepared by cracking
High-purity isobutene is also used to the production of methacrolein and methacrylic acid.Since methyl tertiary butyl ether(MTBE) has water solubility low, resist
Acid strong, inoxidizability is strong, toxicity is low, volatility is low, safety and stability, and the strong feature of solvability, methyl tertiary butyl ether(MTBE) can
It substitutes ether, tetrahydrofuran, aromatic hydrocarbon, methylene chloride equal solvent to use, is the current highest ether of world's annual output, and certain
Continue the main component as clean gasoline in period.
In the prior art, there are many reported in literature for preparing MTBE, MTBE is by isobutene and methanol for the industrial production that routinizes
It carries out addition reaction in the presence of a catalyst to produce to obtain, wherein used catalyst is mainly with styrene-divinylbenzene
Copolymer is the sulfonate resin of matrix, the widest with the use of Amberlyst-15, D72 macroreticular acidic cation exchange resin
General, these spherical copolymer resins have the disadvantage in that reaction temperature is only limitted in the preparation process of methyl tertiary butyl ether(MTBE)
90 DEG C hereinafter, temperature raising can cause resin catalyst to inactivate；Since the reaction is strong exothermal reaction, increase anti-after reaction velocity
It answers temperature to be difficult to be effectively controlled, limits the raising of production capacity；It cannot be regenerated after used resin catalyst inactivation,
Cause catalyst consumption big, it is at high cost, it is unfavorable for environmental protection.
Summary of the invention:
Technical problem to be solved by the present invention lies in overcome the deficiencies in the prior art to provide a kind of methyl tertiary butyl ether(MTBE)
Preparation method.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
A kind of preparation method of methyl tertiary butyl ether(MTBE), comprising the following steps:
(1) pretreatment of carrier: montmorillonite deionized water is infiltrated into 10-30min, surface impurity is removed, is sent into drying
It dries in case to constant weight, crushes, cross 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving is added in the acetum of mass fraction 25-40%, 70-80
DEG C stirring 20-50min；
(3) titanate coupling agent and cumyl peroxide, heating the modification of carrier: are added into step 2 mixed solution
To reflux state, insulated and stirred 0.5-2h is filtered while hot, and solid deionized water and dehydrated alcohol wash away impurity, 50 DEG C of vacuum
Drying arrives modified support to constant weight；
(4) preparation of catalyst: modified support is added in dehydrated alcohol, and tea polyphenols and nano-titanium dioxide is added,
Return stirring 0.5-4h is cooled to 30-35 DEG C of filtering, and 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(5) preparation of methyl tertiary butyl ether(MTBE): the stainless steel of insulating layer fixes the catalyst filling filled band that step 4 obtains
Bed integral reactor, the mixed liquor of the tert-butyl alcohol and methanol is gasified, and vapour enters the fixed bed with insulating layer and integrates
Catalysis reaction is carried out in reactor, the gas-phase product after reaction can be continuously available methyl tertiary butyl ether(MTBE) after condenser condenses,
Incoagulable gas is vented after deep cooling.
The montmorillonite, acetum, titanate coupling agent, cumyl peroxide mass ratio be 20-40:80-
200:5-10:0.1-0.2.
The modified support, tea polyphenols, nano-titanium dioxide mass ratio be 10-20:1-3:1-5.
The mass ratio of the tert-butyl alcohol and methanol is 60-70:80-100 in the tert-butyl alcohol and methyl alcohol mixed liquor.
Existing integral fixedbed reactor in the prior art, the fixed bed can be used in stainless steel integral fixedbed reactor
Integral reactor is needed with insulating layer, and vapour carries out being catalyzed in the integral fixedbed reactor with insulating layer anti-
It answers.
The holding temperature of the insulating layer is 110-120 DEG C.
When acid processing, acetic acid can exchange calcium ion, sodium ion in montmorillonite and form duct, it is made to generate many apertures,
Hydrogen ion can also dissolve the part inorganic ions in alumina octahedral simultaneously, slacken the binding force of interlayer, improve the table of montmorillonite
Face activity；Titanate coupling agent occurs intermolecular coupling, is bonded in montmorillonite under the action of cumyl peroxide simultaneously
In, montmorillonite is promoted to the compatibility and reactivity of organic substance；Under the catalysis of tea polyphenols, nano-titanium dioxide load
In the aperture and interbed of montmorillonite, the two combines the generating rate that can obviously accelerate methyl tertiary butyl ether(MTBE), improves methyl- tert
The purity of butyl ether, while the carrier can repeatedly load use after inactivation.
When the mixed liquor of the tert-butyl alcohol and methanol is gasified, use micro pump by the mixed liquor of the tert-butyl alcohol and methanol with
The air speed indentation evaporator of 0.9-1.0ml/gh gasifies.
The beneficial effects of the present invention are: the activity and stability of prepared catalyst of the present invention are higher than what the prior art used
Styrene-divinylbenzene copolymer is the sulfonate resin of matrix, while can be recycled after catalyst regeneration, obtained product matter
Amount is stablized, and selectivity is good, is suitable for industrialized production.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) pretreatment of carrier: 30g montmorillonite deionized water is infiltrated into 20min, surface impurity is removed, is sent into drying
It dries in case to constant weight, crushes, cross 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving being added in the acetum of 120g mass fraction 30%, and 70 DEG C
Stir 40min；
(3) 6g titanate coupling agent and 0.1g peroxidating diisopropyl the modification of carrier: are added into step 2 mixed solution
Benzene is heated to reflux state, and insulated and stirred 2h is filtered while hot, and solid deionized water and dehydrated alcohol wash away impurity, and 50 DEG C true
Sky drying arrives modified support to constant weight；
(4) preparation of catalyst: 15g modified support is added in dehydrated alcohol, and 1g tea polyphenols and 2g nanometer two is added
Titanium oxide, return stirring 4h are cooled to 32 DEG C of filterings, and 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(5) preparation of methyl tertiary butyl ether(MTBE): the catalyst that step 4 is obtained be filled into specification be D32mm × 2mm ×
600mm has the stainless steel integral fixedbed reactor of insulating layer, with micro pump by the mixed liquor (tert-butyl alcohol of the tert-butyl alcohol and methanol
: methanol=60: 80, mass ratio ratio) gasified with the air speed indentation evaporator of 0.9ml/gh, vapour enters with heat preservation
Catalysis reaction is carried out in the integral fixedbed reactor of layer, the gas-phase product after reaction can be continuously available after condenser condenses
Methyl tertiary butyl ether(MTBE), incoagulable gas are vented after deep cooling.
The selectivity of methyl tertiary butyl ether(MTBE) is 84.7%, and the conversion ratio of the tert-butyl alcohol is 46.9%.
Embodiment 2
(1) pretreatment of carrier: 30g montmorillonite deionized water is infiltrated into 20min, surface impurity is removed, is sent into drying
It dries in case to constant weight, crushes, cross 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving being added in the acetum of 120g mass fraction 30%, and 70 DEG C
Stir 40min；
(3) 6g titanate coupling agent and 0.1g peroxidating diisopropyl the modification of carrier: are added into step 2 mixed solution
Benzene is heated to reflux state, and insulated and stirred 2h is filtered while hot, and solid deionized water and dehydrated alcohol wash away impurity, and 50 DEG C true
Sky drying arrives modified support to constant weight；
(4) preparation of catalyst: 15g modified support is added in dehydrated alcohol, and 1g tea polyphenols and 3g nanometer two is added
Titanium oxide, return stirring 4h are cooled to 32 DEG C of filterings, and 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(5) preparation of methyl tertiary butyl ether(MTBE): the catalyst that step 4 is obtained be filled into specification be D32mm × 2mm ×
600mm has the stainless steel integral fixedbed reactor of insulating layer, with micro pump by the mixed liquor (tert-butyl alcohol of the tert-butyl alcohol and methanol
: methanol=60: 80, mass ratio ratio) gasified with the air speed indentation evaporator of 0.9ml/gh, vapour enters with heat preservation
Catalysis reaction is carried out in the integral fixedbed reactor of layer, the gas-phase product after reaction can be continuously available after condenser condenses
Methyl tertiary butyl ether(MTBE), incoagulable gas are vented after deep cooling.
The selectivity of methyl tertiary butyl ether(MTBE) is 85.0%, and the conversion ratio of the tert-butyl alcohol is 47.3%.
Reference examples 1
(1) pretreatment of carrier: 30g montmorillonite deionized water is infiltrated into 20min, surface impurity is removed, is sent into drying
It dries in case to constant weight, crushes, cross 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving being added in the acetum of 120g mass fraction 30%, and 70 DEG C
Stir 40min；
(3) preparation of catalyst: 15g modified support is added in dehydrated alcohol, and 1g tea polyphenols and 2g nanometer two is added
Titanium oxide, return stirring 4h are cooled to 32 DEG C of filterings, and 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(4) preparation of methyl tertiary butyl ether(MTBE): the catalyst that step 4 is obtained be filled into specification be D32mm × 2mm ×
600mm has the stainless steel integral fixedbed reactor of insulating layer, with micro pump by the mixed liquor (tert-butyl alcohol of the tert-butyl alcohol and methanol
: methanol=60: 80, mass ratio ratio) gasified with the air speed indentation evaporator of 0.9ml/gh, vapour enters with heat preservation
Catalysis reaction is carried out in the integral fixedbed reactor of layer, the gas-phase product after reaction can be continuously available after condenser condenses
Methyl tertiary butyl ether(MTBE), incoagulable gas are vented after deep cooling.
The selectivity of methyl tertiary butyl ether(MTBE) is 70.2%, and the conversion ratio of the tert-butyl alcohol is 28.5%.
Reference examples 2
(1) pretreatment of carrier: 30g montmorillonite deionized water is infiltrated into 20min, surface impurity is removed, is sent into drying
It dries in case to constant weight, crushes, cross 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving being added in the acetum of 120g mass fraction 30%, and 70 DEG C
Stir 40min；
(3) 6g titanate coupling agent and 0.1g peroxidating diisopropyl the modification of carrier: are added into step 2 mixed solution
Benzene is heated to reflux state, and insulated and stirred 2h is filtered while hot, and solid deionized water and dehydrated alcohol wash away impurity, and 50 DEG C true
Sky drying arrives modified support to constant weight；
(4) preparation of catalyst: 15g modified support is added in dehydrated alcohol, and 2g nano-titanium dioxide, reflux is added
4h is stirred, 32 DEG C of filterings are cooled to, 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(5) preparation of methyl tertiary butyl ether(MTBE): the catalyst that step 4 is obtained be filled into specification be D32mm × 2mm ×
600mm has the stainless steel integral fixedbed reactor of insulating layer, with micro pump by the mixed liquor (tert-butyl alcohol of the tert-butyl alcohol and methanol
: methanol=60: 80, mass ratio ratio) gasified with the air speed indentation evaporator of 0.9ml/gh, vapour enters with heat preservation
Catalysis reaction is carried out in the integral fixedbed reactor of layer, the gas-phase product after reaction can be continuously available after condenser condenses
Methyl tertiary butyl ether(MTBE), incoagulable gas are vented after deep cooling.
The selectivity of methyl tertiary butyl ether(MTBE) is 75.1%, and the conversion ratio of the tert-butyl alcohol is 32.4%
Reference examples 3
(1) catalyst: D72 macroreticular acidic cation exchange resin；
(2) preparation of methyl tertiary butyl ether(MTBE): the catalyst that step 4 is obtained be filled into specification be D32mm × 2mm ×
600mm has the stainless steel integral fixedbed reactor of insulating layer, with micro pump by the mixed liquor (tert-butyl alcohol of the tert-butyl alcohol and methanol
: methanol=60: 80, mass ratio ratio) gasified with the air speed indentation evaporator of 0.9ml/gh, vapour enters with heat preservation
Catalysis reaction is carried out in the integral fixedbed reactor of layer, the gas-phase product after reaction can be continuously available after condenser condenses
Methyl tertiary butyl ether(MTBE), incoagulable gas are vented after deep cooling.
The selectivity of methyl tertiary butyl ether(MTBE) is 73.6%, and the conversion ratio of the tert-butyl alcohol is 32.7%.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (5)
1. a kind of preparation method of methyl tertiary butyl ether(MTBE), which comprises the following steps:
(1) pretreatment of carrier: montmorillonite deionized water is infiltrated into 10-30min, surface impurity is removed, is sent into drying box
It after drying to constant weight, crushes, crosses 100-150 mesh；
(2) acidification of carrier: the montmorillonite after sieving being added in the acetum of mass fraction 25-40%, and 70-80 DEG C is stirred
Mix 20-50min；
(3) modification of carrier: titanate coupling agent and cumyl peroxide are added into step 2 mixed solution, is heated to back
Stream mode, insulated and stirred 0.5-2h, is filtered while hot, and solid deionized water and dehydrated alcohol wash away impurity, 50 DEG C of vacuum drying
To constant weight to get arrive modified support；
(4) preparation of catalyst: modified support is added in dehydrated alcohol, and tea polyphenols and nano-titanium dioxide, reflux is added
0.5-4h is stirred, 30-35 DEG C of filtering is cooled to, 50 DEG C are dried under vacuum to constant weight to get catalyst is arrived；
(5) the catalyst filling filled band that step 4 obtains the preparation of methyl tertiary butyl ether(MTBE): is had to the stainless steel fixed bed product of insulating layer
Divide reactor, the mixed liquor of the tert-butyl alcohol and methanol is gasified, vapour enters the fixed bed with insulating layer and integrates reaction
Catalysis reaction is carried out in device, the gas-phase product after reaction can be continuously available methyl tertiary butyl ether(MTBE) after condenser condenses, and not coagulate
Property gas is vented after deep cooling.
2. the preparation method of methyl tertiary butyl ether(MTBE) according to claim 1, it is characterised in that: the montmorillonite, acetic acid are molten
Liquid, titanate coupling agent, cumyl peroxide mass ratio be 20-40:80-200:5-10:0.1-0.2.
3. the preparation method of methyl tertiary butyl ether(MTBE) according to claim 1, it is characterised in that: the modified support, tea are more
Phenol, nano-titanium dioxide mass ratio be 10-20:1-3:1-5.
4. the preparation method of methyl tertiary butyl ether(MTBE) according to claim 1, it is characterised in that: the tert-butyl alcohol and methanol are mixed
Closing the mass ratio of the tert-butyl alcohol and methanol in liquid is 60-70:80-100.
5. the preparation method of methyl tertiary butyl ether(MTBE) according to claim 1, it is characterised in that: the heat preservation temperature of the insulating layer
Degree is 110-120 DEG C.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099072A (en) * | 1988-03-14 | 1992-03-24 | Texaco Chemical Company | Method for one-step synthesis of methyl t-butyl ether |
| US5157161A (en) * | 1991-12-09 | 1992-10-20 | Texaco Chemical Company | One-step synthesis of methyl t-butyl ether from t-butanol using hydrogen fluoride-modified montmorillonite clays |
| US5157162A (en) * | 1991-10-25 | 1992-10-20 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified clay catalysts |
| US5183947A (en) * | 1992-06-19 | 1993-02-02 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified clay catalysts |
| CN106040265A (en) * | 2016-06-13 | 2016-10-26 | 孟红琳 | Method for preparing catalyst for synthesizing methyl tert-butyl ether |
| CN108057458A (en) * | 2016-11-08 | 2018-05-22 | 中国石化扬子石油化工有限公司 | It is a kind of for catalyst of synthesizing methyl tertbutyl ether and its preparation method and application |
-
2018
- 2018-10-30 CN CN201811276815.7A patent/CN109232196B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099072A (en) * | 1988-03-14 | 1992-03-24 | Texaco Chemical Company | Method for one-step synthesis of methyl t-butyl ether |
| US5157162A (en) * | 1991-10-25 | 1992-10-20 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified clay catalysts |
| US5157161A (en) * | 1991-12-09 | 1992-10-20 | Texaco Chemical Company | One-step synthesis of methyl t-butyl ether from t-butanol using hydrogen fluoride-modified montmorillonite clays |
| US5183947A (en) * | 1992-06-19 | 1993-02-02 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified clay catalysts |
| CN106040265A (en) * | 2016-06-13 | 2016-10-26 | 孟红琳 | Method for preparing catalyst for synthesizing methyl tert-butyl ether |
| CN108057458A (en) * | 2016-11-08 | 2018-05-22 | 中国石化扬子石油化工有限公司 | It is a kind of for catalyst of synthesizing methyl tertbutyl ether and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 金晓农等: "合成甲基叔丁基醚催化剂的研究", 《离子交换与吸附》 * |
| 高占笙等: "甲醇和叔丁醇一步合成甲基叔丁基醚", 《齐鲁石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031485A (en) * | 2021-12-03 | 2022-02-11 | 山东成泰新材料有限公司 | Method for synthesizing methyl tert-butyl ether |
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