CN105536870A - Catalyst for synthesizing methyl tert-butyl ether and preparation method for methyl tert-butyl ether - Google Patents

Catalyst for synthesizing methyl tert-butyl ether and preparation method for methyl tert-butyl ether Download PDF

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Publication number
CN105536870A
CN105536870A CN201510965180.1A CN201510965180A CN105536870A CN 105536870 A CN105536870 A CN 105536870A CN 201510965180 A CN201510965180 A CN 201510965180A CN 105536870 A CN105536870 A CN 105536870A
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butyl ether
catalyst
heteropoly acid
mtbe
methyl tert
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崔贤长
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08Ion-exchange resins
    • B01J31/10Ion-exchange resins sulfonated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/05Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/3411,2-additions, e.g. aldol or Knoevenagel condensations
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a catalyst for synthesizing methyl tert-butyl ether and a preparation method for the methyl tert-butyl ether. The method comprises the steps of firstly subjecting raw materials, i.e., residual C4 and methanol for preparing the methyl tert-butyl ether to rectification, and then, subjecting isobutene in the residual C4 and methanol to an etherification reaction in a solid-bed mixed-phase reactor in a manner of taking heteropoly acid H4SiW12O40 immobilized on macroporous cation exchange resin as a catalyst, thereby obtaining the methyl tert-butyl ether. The catalyst can be used for increasing the conversion ratio of isobutene, has relatively large specific surface area and high protonic acid strength, does not corrode equipment substantially, is easy to recover, can be reused and is environment-friendly, so that industrial production is facilitated.

Description

A kind of Catalysts and its preparation method for the synthesis of methyl tertiary butyl ether(MTBE)
Technical field
The present invention relates to a kind of Catalysts and its preparation method for the synthesis of methyl tertiary butyl ether(MTBE), devise a kind of heteropoly acid especially immobilized in the preparation method of large aperture resin cation, and be applied to methyl tertiary butyl ether(MTBE) synthesis technique, belong to petroleum chemical industry field.
Background technology
Methyl tertiary butyl ether(MTBE) (methyltert-butylether, MTBE) be a kind of high-knock rating gasoline additive, after adding MTBE in gasoline, the octane number of gasoline can not only be improved, the train operation performance of automobile can also be improved, replace lead tetraethide with MTBE and can also reduce CO discharge capacity, reduce the pollution to environment.The carbon four that MTBE is also a kind of not burn into low stain, cost is low is separated new tool.The isobutene polymer grade that cracking obtains, can prepare butyl rubber.Decomposed by MTBE, the isobutene of gained only needs, through simply distilling and washing, can obtain the high-purity isobutylene of 99.55%.
At present, the catalyst that production MTBE production technology generally adopts both at home and abroad is ion exchange resin, and the earliest, technical comparative maturity, adopt a device single tower process, energy consumption is low, economical for this method commercial Application.The conventional external trade mark is Ambeilyst-15(A-15), the domestic trade mark is S type and D type.This large aperture strong acidic ion resin catalyst be by sulfonated phenylethylene and divinylbenzene in proportion by the copolymer catalyst granules that suspension polymerization generates, obtain after acidified process.But it is short that this catalyst still exists life cycle, poor heat stability, sulfonic group comes off and easily causes the problems such as equipment corrosion.
In recent years, heteropoly acid has complex and metal oxide structures feature concurrently, have again highly acid and oxidation-reduction quality concurrently, the catalyst having researching value and DEVELOPMENT PROSPECT most, Keggin-type heteropoly acid, because of Stability Analysis of Structures, acidity is strong, catalytic performance is excellent, to the selective height of MTBE, environmentally safe, has the advantages such as " false liquid phase " behavior, obtains research and apply widely.
When heteropoly acid makees catalyst in liquid homogeneous phase catalytic reaction, because its surface area is less, need products of separated and catalyst in last handling process, cost is caused to increase, in commercial Application, heteropoly acid is carried out immobilized, its catalytic activity, selective, conversion ratio can not only be improved, also make the separation process of product and catalyst be simplified.
Publication number CN1304798A patent discloses a kind of molecular sieve catalyst for the synthesis of methyl tertiary butyl ether(MTBE) and preparation method thereof, catalyst is made up of molecular sieve and heteropoly acid, and catalyst isobutene maximum conversion reaches 97%, selective good (MTBE is selective is 92% ~ 98%), life-span long (micro-anti-experimental lifetime best catalyst performance in 720 hours do not change).
The bibliographical information immobilized silicon tungsten of a kind of active carbon (SiW 12) and phosphorus tungsten (PW 12) preparation method of heteropoly acid, and catalyzing and synthesizing MTBE and ETBE in the gas phase, this catalyst synthesis MTBE has higher catalytic activity (conversion ratio of isobutene is about 50%) and selective (100%).(Chu Wenling etc. active carbon solid-carrying heteropolyacid gas phase catalytic synthesis methyl tertiary butyl ether(MTBE) and ethyl tert-butyl ether (ETBE), petrochemical industry, 25 volumes in 1996,462 ~ 467).
Bibliographical information a kind of with the tert-butyl alcohol and methyl alcohol for raw material, the method of methyl tertiary butyl ether(MTBE) (MTBE) has been synthesized under silver salt heteropoly acid (AgPA) catalysis, this catalyst has higher conversion ratio and selective, and be a kind of material being insoluble to reactant, when catalyst amount is 5g, conversion ratio can reach 35.03%, selectively reaches 68.3%, as long as this catalyst dry 12h under 50 DEG C of vacuum conditions just can re-use by activity recovery completely.(kingdom is safe, the research [J] of heteropoly acid catalysis synthesize methyl tert-butyl ether. Shaanxi chemical industry, 1998,27(3) and 30 ~ 31,38.).
Bibliographical information is a kind of has the heteropoly acid of structure with Keggin for catalyst with immobilized on bentonite four kinds, have studied their activity at gas phase catalytic synthesis methyl tertiary butyl ether(MTBE), catalyst is 100% to generation the selective of methyl tertiary butyl ether(MTBE) in the reaction, with HZSM-5 and Ion Exchange Resin Phase ratio, immobilized have higher catalytic activity in bentonitic heteropoly acid, and the conversion ratio of isobutene is about 50%.
In above-mentioned disclosed technology, for the synthesis of the heteropolyacid catalyst of methyl tertiary butyl ether(MTBE), substantially be adopt simple heteropoly acid or by the inorganic carriers such as loaded by heteropoly acid and active carbon, bentonite, molecular sieve, the macroreticular structure that these carriers do not have resin catalyst styrene and divinylbenzene to be formed under appropriate pore-foaming agent effect, active on the low side.Countless reticulated channel in macroreticular resin carrier add the contact in reaction mass and activated centre, and large aperture is conducive to reaction, and is conducive to the obstruction preventing dimer byproduct.
Summary of the invention
The object of this invention is to provide and a kind ofly prepare the method for the catalyst of methyl tertiary butyl ether(MTBE) and the application on synthesize methyl tert-butyl ether thereof, the heteropolyacid catalyst of this method working load and large aperture resin, MTBE productive rate can be improved, product purity is improved, reduce environmental pollution.
The invention provides a kind of Catalysts and its preparation method for the synthesis of methyl tertiary butyl ether(MTBE), comprise the following steps: residual C4 enters head tank, material benzenemethanol enters methanol feedstock tank, mix after two kinds of materials are pressurizeed respectively, the impurity such as mixed material enters a counter ion filter, removing metal cation, are then preheating to 45 ~ 65 DEG C by material, enter fixed bed mixed phase reactor, in reactor, add heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin, at 60 ~ 70 DEG C, carry out etherification reaction generate methyl tertiary butyl ether(MTBE).The material of reactor bottom is sent into primary distillation tower, and MTBE bottom primary distillation tower, through being cooled to 40 DEG C, enters surge tank, detect qualified after enter tank field.
Isobutene in raw material residual C4 described in invention and methyl alcohol mixing mol ratio are 1.05 ~ 1.2:1.In residual C4, the content of isobutene is 15 ~ 35%.
Heteropoly acid H described in invention 4siW 12o 40large aperture cationic ion-exchange resin prepared by following preparation method: at 1m 3the Amberlyst15(A-15 of drying to constant weight is added in hot pressure reaction still) type ion exchange resin, and add the heteropoly acid H of 30% ~ 50% of amount of resin quality 4siW 12o 40, soak in mixed solution, in 105 ~ 120 DEG C of reaction 15 ~ 24h, then washing is for neutral, and vacuum filtration removing moisture, is dried to constant weight at 105 ~ 120 DEG C.
Heteropoly acid H described in invention 4siW 12o 40large aperture cationic ion-exchange resin can also be prepared by following preparation method: vacuum drying is joined heteropoly acid H to the Amberlyst15 of constant weight 4siW 12o 40toluene solution in, stirred at ambient temperature 24h, is dried to constant weight after filtration at ambient temperature, and at 120 DEG C, roasting 2h, namely obtains target product.
Mixed solution described in invention consists of toluene, dimethylbenzene, acetone and other organic solvent and mixes with water obtained, and the mol ratio of organic solvent and water is 1:1.5.
Method provided by the invention, adopt fixed bed mixed phase reactor, the conversion ratio that can improve isobutene effectively controls the temperature of reaction bed, energy-saving and cost-reducing.
The carried heteropoly acid catalyst that the present invention adopts, catalytic activity high, selective good, accessory substance is few, good product quality, yield are high, technique simply and not etching apparatus, reduces production cost, is easy to suitability for industrialized production.And catalyst can reclaim, regenerate recycling.
Method provided by the invention, adopt loaded by heteropoly acid on A-15 as the catalyst of synthesize methyl tert-butyl ether, its specific activity A-15 catalyst activity is high, and its activity is higher than on loaded by heteropoly acid and active carbon, and selective all close to 100% to MTBE of this catalyst.Its high activity interacts and is formed due to heteropoly acid and load.Large aperture resin carrier provides countless reticulated channel, high pore volume and large specific area very favourable to etherification reaction, improve the contact of reaction mass and catalyst, be conducive to improving catalytic activity, and large aperture is conducive to the obstruction preventing dimer byproduct.
Detailed description of the invention
Below in conjunction with embodiment, technical characteristic of the present invention is further described, but the present invention being not limited to the following example, not departing under teachings of the present invention, change of the present invention being included in technical scope of the present invention.
Embodiment 1: the preparation of catalyst
At 1m 3the Amberlyst15(A-15 of drying to constant weight is added in hot pressure reaction still) type ion exchange resin, and add the heteropoly acid H of 50% of amount of resin quality 4siW 12o 40, in mixed solution, soak (mixed solution consists of acetone: water=1:1.2), in 110 DEG C of reaction 20h, then washing is for neutral, and vacuum filtration removing moisture, is dried to constant weight at 110 DEG C.The total acid content that molten solvent method tests this catalyst is 3.8541mmol/g.
Embodiment 2: the preparation of catalyst
At 1m 3the Amberlyst15(A-15 of drying to constant weight is added in hot pressure reaction still) type ion exchange resin, and add the heteropoly acid H of 30% of amount of resin quality 4siW 12o 40, in mixed solution, soak (mixed solution consists of toluene: water=1:1.2), in 105 DEG C of reaction 24h, then washing is for neutral, and vacuum filtration removing moisture, is dried to constant weight at 105 DEG C.The total acid content testing this catalyst with solvent method is 3.7364mmol/g.
Embodiment 3: the preparation of catalyst
At 1m 3the Amberlyst15(A-15 of drying to constant weight is added in hot pressure reaction still) type ion exchange resin, and add the heteropoly acid H of 50% of amount of resin quality 4siW 12o 40, in mixed solution, soak (mixed solution consists of dimethylbenzene: water=1:1.5), in 120 DEG C of reaction 18h, then washing is for neutral, and vacuum filtration removing moisture, is dried to constant weight at 120 DEG C.The total acid content measuring this catalyst with solvent method is 3.9068mmol/g.
Embodiment 4: the preparation of catalyst
Vacuum drying is joined heteropoly acid H to the Amberlyst15 of constant weight 4siW 12o 40toluene solution in, stirred at ambient temperature 24h, is dried to constant weight after filtration at ambient temperature, and at 120 DEG C, roasting 2h, namely obtains catalyst, and the total acid content measuring this catalyst through solvent method is 4.5620mmol/g.
Embodiment 5: the synthesis of methyl tertiary butyl ether(MTBE)
Residual C4 enters head tank, and material benzenemethanol enters methanol feedstock tank, mixes after being pressurizeed respectively by two kinds of materials, the impurity such as mixed material enters counter ion filter, removing metal cation, are then preheating to 50 DEG C by material, enter fixed bed mixed phase reactor, in reactor, add heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin (embodiment 1), 60 DEG C carry out etherification reaction generate methyl tertiary butyl ether(MTBE).The material of reactor bottom is sent into primary distillation tower, and MTBE bottom primary distillation tower, through being cooled to 40 DEG C, enters surge tank, detect qualified after enter tank field.Passing through and calculating isobutene conversion is 62.5%, and catalyst is 99.8% to the selective of MTBE.
Embodiment 6: the synthesis of methyl tertiary butyl ether(MTBE)
Residual C4 enters head tank, and material benzenemethanol enters methanol feedstock tank, mixes after being pressurizeed respectively by two kinds of materials, the impurity such as mixed material enters counter ion filter, removing metal cation, are then preheating to 65 DEG C by material, enter reactor, in fixed bed mixed phase reactor, add heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin (embodiment 4), 70 DEG C carry out etherification reaction generate methyl tertiary butyl ether(MTBE).The material of reactor bottom is sent into primary distillation tower, and MTBE bottom primary distillation tower, through being cooled to 40 DEG C, enters surge tank, detect qualified after enter tank field.Isobutene conversion is 60.2% as calculated, and catalyst is 99.6% to the selective of MTBE.

Claims (6)

1. for the synthesis of a Catalysts and its preparation method for methyl tertiary butyl ether(MTBE), it is characterized in that, comprise the following steps:
Residual C4 enters head tank, and material benzenemethanol enters methanol feedstock tank, mixes after being pressurizeed respectively by two kinds of materials, the impurity such as mixed material enters counter ion filter, removing metal cation, are then preheating to 45 ~ 65 DEG C by material, enter fixed bed mixed phase reactor, in reactor, add heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin, at 60 ~ 70 DEG C, carry out etherification reaction generate methyl tertiary butyl ether(MTBE),
The material of reactor bottom is sent into primary distillation tower, and MTBE bottom primary distillation tower, through being cooled to 40 DEG C, enters surge tank, detect qualified after enter tank field.
2. method according to claim 1, is characterized in that, adopt fixed bed mixed phase reactor, the conversion ratio that can improve isobutene effectively controls the temperature of reaction bed, energy-saving and cost-reducing.
3. method according to claim 1, is characterized in that, the isobutene in described raw material residual C4 and methyl alcohol mixing mol ratio are 1.05 ~ 1.2:1, and in residual C4, the content of isobutene is 15 ~ 35%.
4. method according to claim 1, is characterized in that, described heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin prepared by following preparation method:
At 1m 3the Amberlyst15(A-15 of drying to constant weight is added in hot pressure reaction still) type ion exchange resin, and add the heteropoly acid H of 30% ~ 50% of amount of resin quality 4siW 12o 40, soak in mixed solution, in 105 ~ 120 DEG C of reaction 15 ~ 24h, then washing is for neutral, and vacuum filtration removing moisture, is dried to constant weight at 105 ~ 120 DEG C.
5. method according to claim 1, is characterized in that, described heteropoly acid H 4siW 12o 40large aperture cationic ion-exchange resin can also be prepared by following preparation method:
Vacuum drying is joined heteropoly acid H to the Amberlyst15 of constant weight 4siW 12o 40toluene solution in, stirred at ambient temperature 24h, is dried to constant weight after filtration at ambient temperature, and at 120 DEG C, roasting 2h, namely obtains target product.
6. method according to claim 3, is characterized in that, described mixed solution consists of toluene, dimethylbenzene, acetone and other organic solvent and mixes with water obtained, and the mol ratio of organic solvent and water is 1:1.5.
CN201510965180.1A 2015-12-21 2015-12-21 Catalyst for synthesizing methyl tert-butyl ether and preparation method for methyl tert-butyl ether Pending CN105536870A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020022749A1 (en) * 1998-12-22 2002-02-21 Gracey Benjamin Patrick Process for making butyraldehyde from butadiene
CN1781598A (en) * 2004-11-30 2006-06-07 中国石油化工股份有限公司 Method for preparing resin assembled heteropoly acid salt catalyst
CN101190860A (en) * 2006-11-30 2008-06-04 中国石油化工股份有限公司 Dimerization-etherification method for producing MTBE, isooctene and diisobutylene from C4 olefin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020022749A1 (en) * 1998-12-22 2002-02-21 Gracey Benjamin Patrick Process for making butyraldehyde from butadiene
CN1781598A (en) * 2004-11-30 2006-06-07 中国石油化工股份有限公司 Method for preparing resin assembled heteropoly acid salt catalyst
CN101190860A (en) * 2006-11-30 2008-06-04 中国石油化工股份有限公司 Dimerization-etherification method for producing MTBE, isooctene and diisobutylene from C4 olefin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TOSHIHIDE BABA ET AL.: "Heteropoly acids supported on acidic ion-exchange resin as highly active solid-acid catalysts", 《BULL.CHEM.SOC.JPN.》 *
化工一厂甲丁车间: "《MTBE装置生产原理及工艺流程》", 12 July 2011 *

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Application publication date: 20160504