CN104326871A - Preparation method for butanediol - Google Patents
Preparation method for butanediol Download PDFInfo
- Publication number
- CN104326871A CN104326871A CN201410531949.4A CN201410531949A CN104326871A CN 104326871 A CN104326871 A CN 104326871A CN 201410531949 A CN201410531949 A CN 201410531949A CN 104326871 A CN104326871 A CN 104326871A
- Authority
- CN
- China
- Prior art keywords
- butylene
- acetic acid
- bdo
- preparation
- butylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
Abstract
The invention discloses a preparation method for butanediol, wherein the preparation method comprises the following steps of adopting a fixed bed catalytic technology, mixing 2-butene having the content of more than 99% with acetic acid, nitrogen, oxygen and water vapor at high temperature, and then introducing into a fixed bed; the preparation method greatly reduces the environmental pressure of industrial products, and puts forward a new thinking and a new method for achieving continuous development of petrochemical industries.
Description
Technical field
The present invention relates to a kind of preparation method of butyleneglycol.
Background technology
Current production 1, the route of 4-butyleneglycol is numerous, has the Reppe method with acetylene, formaldehyde, the Mitsubishi's forming technology being raw material with divinyl and acetic acid, take vinylcarbinol as the Kuraray technology of raw material, and be two-step approach (Davy-Mckee) and the single stage method (GEMINOX) of raw material with normal butane.Various route is each has something to recommend him, is all the current industrialized important method of BDO.
Along with the tremendous development of China's ethylene industry, add the rapid growth of China's refinery industry, c4 fraction annual amount is more than 2 megatons, and 1-butylene wherein, divinyl and iso-butylene product seriation have become the main flow of carbon four processing and utilization.Starting successively of domestic MTBE device, after particularly precise distillation isolates 1-butylene, in by-product carbon four, the content of 2-butylene can reach 80%, this part product is substantially all as fuel treatment at present, industrial value is lower, develop a kind of 2-butylene deep processing and utilization technique device, more economical Appropriate application 2-butylene method has become one of major technique focal issue of carbon four deep processing.
Summary of the invention
The present invention is the deficiency in order to solve background technology, provides a kind of catalysis 2-butylene to synthesize the technological method of BDO, to solve the deep exploitation problem of 2-butylene in petrochemical complex by-product carbon four component.
1, the object of the invention is to realize as follows: a kind of preparation method of butyleneglycol, the steps include:
A, adopt fixed-bed catalytic technology, pass in fixed bed after 2-butylene content being greater than 99% mixes with acetic acid, nitrogen, oxygen and water vapor high temperature, reaction conditions is:
Pressure 0.3-1.6MPa, 2-butylene: nitrogen: oxygen: acetic acid: water vapor=1:6:0.5:8:5
Temperature of reaction: 130-220 DEG C
Reaction 2-butylene transformation efficiency: >92%
Two acetic acid 2-butylene alcohol ester selectivity: >94%:
The volatile component of decompression removing after B, product condensation, can obtain the acetic acid of BDO crude product and recyclable recycling with hydrolyzed under acidic conditions, concrete synthesis condition is:
Acidic conditions, pH value is less than 4
Water: two acetic acid 2-butylene alcohol ester (mol ratio)=12-24.5:1
Hydrolysis obtains butylene glycol molar yield and is greater than 98%;
C, the butylene glycol obtained to be refined, obtain more than 99.5% butylene glycol sterling, with 5-10% palladium chtalyst hydrogenation, crude product BDO can be obtained, this step butylene glycol transformation efficiency >95%, BDO selectivity 100%;
D, the crude product BDO obtained to be refined.
Advantage of the present invention: the present invention adopts the carbon four component direct production processing 1 in petrochemical industry, 4-butyleneglycol, particularly use in the industry of current carbon four and directly process 1 for the by-product 2-butylene of gas conditioning in a large number, 4-butyleneglycol, not only be conducive to the raw-material Appropriate application of petrochemical industry, increase the utility value of 2-butylene in carbon four component, and significantly reduce the environmental stress of these Industrial products, for the realized development realizing petrochemical industry proposes new approaches novel method.
embodiment:
1, a preparation method for butyleneglycol, its preparation process is:
A, adopt fixed-bed catalytic technology, pass in fixed bed after 2-butylene content being greater than 99% mixes with acetic acid, nitrogen, oxygen and water vapor high temperature, reaction conditions is:
Pressure 0.3-1.6MPa, 2-butylene: nitrogen: oxygen: acetic acid: water vapor=1:6:0.5:8:5
Temperature of reaction: 130-220 DEG C
Reaction 2-butylene transformation efficiency: >92%
Two acetic acid 2-butylene alcohol ester selectivity: >94%:
The volatile component of decompression removing after B, product condensation, can obtain the acetic acid of BDO crude product and recyclable recycling with hydrolyzed under acidic conditions, concrete synthesis condition is:
Acidic conditions, pH value is less than 4
Water: two acetic acid 2-butylene alcohol ester (mol ratio)=12-24.5:1
Hydrolysis obtains butylene glycol molar yield and is greater than 98%;
C, the butylene glycol obtained to be refined, obtain more than 99.5% butylene glycol sterling, with 5-10% palladium chtalyst hydrogenation, crude product BDO can be obtained, this step butylene glycol transformation efficiency >95%, BDO selectivity 100%;
D, the crude product BDO obtained to be refined.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1. a preparation method for butyleneglycol, its preparation process is:
A, adopt fixed-bed catalytic technology, pass in fixed bed after 2-butylene content being greater than 99% mixes with acetic acid, nitrogen, oxygen and water vapor high temperature, reaction conditions is:
Pressure 0.3-1.6MPa, 2-butylene: nitrogen: oxygen: acetic acid: water vapor=1:6:0.5:8:5
Temperature of reaction: 130-220 DEG C
Reaction 2-butylene transformation efficiency: >92%
Two acetic acid 2-butylene alcohol ester selectivity: >94%:
The volatile component of decompression removing after B, product condensation, can obtain the acetic acid of BDO crude product and recyclable recycling with hydrolyzed under acidic conditions, concrete synthesis condition is:
Acidic conditions, pH value is less than 4
Water: two acetic acid 2-butylene alcohol ester (mol ratio)=12-24.5:1
Hydrolysis obtains butylene glycol molar yield and is greater than 98%;
C, the butylene glycol obtained to be refined, obtain more than 99.5% butylene glycol sterling, with 5-10% palladium chtalyst hydrogenation, crude product BDO can be obtained, this step butylene glycol transformation efficiency >95%, BDO selectivity 100%;
D, the crude product BDO obtained to be refined.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410531949.4A CN104326871A (en) | 2014-10-11 | 2014-10-11 | Preparation method for butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410531949.4A CN104326871A (en) | 2014-10-11 | 2014-10-11 | Preparation method for butanediol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104326871A true CN104326871A (en) | 2015-02-04 |
Family
ID=52401697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410531949.4A Pending CN104326871A (en) | 2014-10-11 | 2014-10-11 | Preparation method for butanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104326871A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892363A (en) * | 2015-06-15 | 2015-09-09 | 江苏常州酞青新材料科技有限公司 | Method for preparing butanediol |
| CN107774250A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst for 1,4 diacetoxy butylene hydrogenation techniques |
| CN107774253A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | For synthesizing the hydrogenation catalyst of 1,4 diacetoxy butane |
| CN107774251A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Manufacture the hydrogenation catalyst of 1,4 diacetoxy butane |
| CN107774336A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst for 1,4 diacetoxy butylene hydrogenation processes |
| CN107913704A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The hydrogenation catalyst of 1,4 diacetoxy butane of butadiene production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100361A (en) * | 1975-10-11 | 1978-07-11 | Basf Aktiengesellschaft | Manufacture of butenediol diacetates |
| US4262139A (en) * | 1978-10-28 | 1981-04-14 | Basf Aktiengesellschaft | Preparation of butenediol diacetates and of butanediol |
| CN1172792A (en) * | 1996-06-24 | 1998-02-11 | 林德股份公司 | Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation |
| CN102834370A (en) * | 2010-02-16 | 2012-12-19 | 株式会社Api | Method for producing 1-amino-1-alkoxycarbonyl-2-vinylcyclopropane |
-
2014
- 2014-10-11 CN CN201410531949.4A patent/CN104326871A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100361A (en) * | 1975-10-11 | 1978-07-11 | Basf Aktiengesellschaft | Manufacture of butenediol diacetates |
| US4262139A (en) * | 1978-10-28 | 1981-04-14 | Basf Aktiengesellschaft | Preparation of butenediol diacetates and of butanediol |
| CN1172792A (en) * | 1996-06-24 | 1998-02-11 | 林德股份公司 | Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation |
| CN102834370A (en) * | 2010-02-16 | 2012-12-19 | 株式会社Api | Method for producing 1-amino-1-alkoxycarbonyl-2-vinylcyclopropane |
Non-Patent Citations (1)
| Title |
|---|
| 刘新波: "1，4－丁二醇生产工艺及市场分析", 《化工中间体》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892363A (en) * | 2015-06-15 | 2015-09-09 | 江苏常州酞青新材料科技有限公司 | Method for preparing butanediol |
| CN107774250A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst for 1,4 diacetoxy butylene hydrogenation techniques |
| CN107774253A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | For synthesizing the hydrogenation catalyst of 1,4 diacetoxy butane |
| CN107774251A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Manufacture the hydrogenation catalyst of 1,4 diacetoxy butane |
| CN107774336A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst for 1,4 diacetoxy butylene hydrogenation processes |
| CN107774336B (en) * | 2016-08-29 | 2019-10-08 | 中国石油化工股份有限公司 | Catalyst for 1,4- diacetoxy butylene hydrogenation process |
| CN107774253B (en) * | 2016-08-29 | 2019-10-11 | 中国石油化工股份有限公司 | For synthesizing the hydrogenation catalyst of 1,4- diacetoxy butane |
| CN107774250B (en) * | 2016-08-29 | 2019-10-11 | 中国石油化工股份有限公司 | Catalyst for 1,4- diacetoxy butylene hydrogenation technique |
| CN107913704A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The hydrogenation catalyst of 1,4 diacetoxy butane of butadiene production |
| CN107913704B (en) * | 2016-10-09 | 2020-02-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for producing 1, 4-diacetoxybutane from butadiene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104326871A (en) | Preparation method for butanediol | |
| CN102992933B (en) | A kind of separation method of mixed c 4 | |
| CN101555197B (en) | Comprehensive use method of mixed C-4 | |
| CN102690172A (en) | Method for producing isopropanol by acetone hydrogenation | |
| CN101402553B (en) | Method for producing high purity MTBE with C4 and methanol | |
| CN102633588B (en) | Method for preparing high-purity isobutene from raffinate C4 by means of separation | |
| CN205115334U (en) | Xylene production system | |
| CN102134191A (en) | Process method for producing ethyl acetate by catalytic rectification | |
| CN103910601B (en) | Method for producing monohydric alcohol from water and olefins | |
| CN101811928B (en) | Method for preparing isopropyl benzene | |
| CN104892363A (en) | Method for preparing butanediol | |
| CN205115333U (en) | Energy -saving xylol production system | |
| CN102070390B (en) | The method of refinery's mixed c 4 propylene | |
| CN103387495A (en) | Method for the continuous production of carboxylic acid esters | |
| CN104262189A (en) | Method for liquid-phase preparation of high-purity N, N-diethylformamide | |
| CN103130633A (en) | Method for producing p-methylacetophenone with fixed-bed reactor | |
| CN103787877B (en) | Preparation method of cyclohexyl acetate | |
| CN102285857B (en) | Method for increasing yields of propylene and ethylene | |
| CN205061923U (en) | Increase production etherificate ether of high -purity isobutene and separate combination unit | |
| CN103360208B (en) | Be separated the method for acetal in BDO | |
| CN103304362A (en) | Preparation method of high purity cyclopentene | |
| CN103304361A (en) | Production method of high purity cyclopentene | |
| CN102649670A (en) | Method for preparing ethylene through dehydration of ethanol | |
| CN103254042A (en) | Technique for synthesizing dimethyl ether | |
| CN104030877B (en) | A kind of preparation method of propylene dimer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150204 |