CN101337858B - Process and equipment for preparing 1,2-butadiene by continuous method - Google Patents
Process and equipment for preparing 1,2-butadiene by continuous method Download PDFInfo
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- CN101337858B CN101337858B CN2007100433883A CN200710043388A CN101337858B CN 101337858 B CN101337858 B CN 101337858B CN 2007100433883 A CN2007100433883 A CN 2007100433883A CN 200710043388 A CN200710043388 A CN 200710043388A CN 101337858 B CN101337858 B CN 101337858B
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Abstract
The invention discloses a process technique and a separation plant for continuously preparing styrene-butadiene rubber inhibitor by a separation method. The process comprises the following steps: selecting heavy components of the byproduct of 1,3-butadiene produced by the extraction method as the raw material containing 1,2-butadiene 5 to 12% (wt), washing with water to remove the trace amount of a residual solvent, removing the heavy component and the light component on the same rectification tower by a common rectification method with side withdrawing, rectifying at a kettle temperature of 55 to 65 DEG C and a sensitive plate temperature of 52 to 62 DEG C, under 0.35 to 0.39 MPa and in an oxygen-free condition; adding a proper amount of polymerization inhibitor, and continuously withdrawing the product containing 1,2-butadiene with an amount equal to or larger than 40%. The method can obviate the problems in the production technology, the safety, the environment protection, etc. resulting from the factors such as the raw material, the catalyst and the byproducts, and also increase the additional value of the 1,3-butadiene byproducts, thereby achieving remarkable economic and social benefits.
Description
Technical field
The present invention relates to prepare continuously the Technology and the separating device of styrene-butadiene rubber(SBR) inhibitor 1 with partition method.
Background technology
In the successive polymerization of solution styrene butadiene rubber is produced, because understanding some in continuous polymerization process, the living chain that organolithium caused forms gel, gel content in the rubber is significantly risen, quality product descends, and these gels also can be deposited on some position of reactor, and continue reaction with monomer and form the gel micelle of bulk, cause reactor plugs, have a strong impact on production.Therefore, must adding in the solution styrene butadiene rubber successive polymerization is produced to produce the gel inhibitor of chain transfer, suppress the gel generation and do not reduce monomer conversion, do not influence rubber performance by the conditioned reaction dynamic process.
1 is the special-purpose a kind of gel inhibitor of solution styrene butadiene rubber successive polymerization industrial installation (French Bayer company-former U.S. Firestone company France factory, U.S. Firestone company, the company of Japanese Asahi Chemical Industry of belonging to) in the world at present.
From documents and materials, less to the relevant report of 1 preparation at present.Only there are several pieces of patent documentations to relate to 1, the preparation of 2-divinyl, disclose a kind of as US3751511 by thereby isomerization makes 1 to 2-butyne, the operational path of 2-divinyl, it promptly is raw material with the 2-butyne, with first and second main group element (potassium, lithium, caesium, rubidium, magnesium etc.), and the catalyzer of Fatty Alcohol(C12-C14 and C12-C18) (methyl alcohol, ethanol, propyl alcohol etc.) composition.Under 20-40 ℃ of condition, react, can make 1.This report is described in detail various selection of catalysts is used.Wherein using maximum is tert.-butoxy potassium.Being catalyzer with tert.-butoxy potassium and the inferior maple of diformazan for example, is raw material with the 2-butyne, and reaction is 7 hours under 27 ℃ condition, can obtain 1.
There was report in Japan in disclosed patent specification on October 29th, 1984 (clear 59-190929), oxyhydroxide and positively charged ion solvent at basic metal are under the condition of catalyst, by the 2-butyne isomerization is made 1, the manufacture method of 3-divinyl and 1,2 divinyl (following common name butadiene type).
Be used as the oxyhydroxide of basic metal, sodium hydroxide, potassium hydroxide, lithium hydroxide etc. are arranged.Sodium hydroxide, potassium hydroxide high reactivity low price are more satisfactory.In addition, the oxyhydroxide of basic metal can hang turbid or be dissolved in the solvent.Perhaps can use aluminite, silica, gac, general carrier such as magnesium oxide and zeolite.
There was report (1881-1882the chemical society ofJapan) in the chemical association of Japan in nineteen eighty-two, was raw material with all kinds of alkynes, with CaO, SrO, La
2O
3Deng being catalyzer, after higher temperature (about 600 ℃) causes down, carry out isomerization reaction, can make 1,2 divinyl.
Also have report in addition, adopt sulfonyloxy methyl base class material to carry out reductive technology and make the method for 1.
Take a broad view of above various preparation methods, its common ground all is that to adopt certain monomer or compound be raw material, by selection and the optimization to different catalysts, carries out isomery, reduction, decomposition, chemical reaction such as synthetic under certain temperature, pressure condition, make 1 then.In these preparation technologies, to the selection of raw material, the steps such as processing of pre-treatment, reaction residue are all had relatively high expectations; Some also relates to the restriction of rules such as environmental protection, safety; And all be step.Because 1 just uses as special-purpose gel inhibitor in the solution styrene butadiene rubber successive polymerization is produced, and does not temporarily also have other purposes.So, the report of this respect new technology, new technology route is seldom arranged.
100,000 tons of/year solution styrene butadiene rubber successive polymerization production equipments of the newly-built operation of heightization corporatization worker division department are the production technologies of introducing company of Japanese Asahi Chemical Industry.This matching requirements uses 1 as gel inhibitor.In view of domestic and international present 1 production technology situation, will there be source of goods problem in the 1 external as import, need further to implement; As introducing technology, will pay the technology expense of great number, and uneconomical, but do not have the 1 source, can directly have influence on 100,000 tons of/year solution styrene butadiene rubber devices again go into operation smoothly.Under this background, the preparation technology who develops, works out a kind of economic, practical, feasible 1 as soon as possible becomes the task of a most important thing.
Summary of the invention
Problem to be solved by this invention is the preparation technology of the 1 of a kind of new simple, safety of exploitation, environmental protection, for 100,000 tons of/year newly-built solution styrene butadiene rubber devices provide the gel inhibitor 1.Thinking of the present invention is: the Technology that adopts chemical separating, with chemical industry division department 1, by product heavy constituent in the 3-divinyl extracting production process are (hereinafter to be referred as heavy constituent, include 1 of the 5-12% that has an appointment, the 2-divinyl) is raw material, wherein part 1 is extracted, obtain the production technology of qualified 1 by washing, rectifying, drying.
The technical solution used in the present invention is as follows: the by product reorganization of producing 1,3-butadiene with extraction process is divided into raw material, comprises the steps:
1) washing, the trace solvent of flush away remnants, washing tower top pressure 0.43～0.47Mpa, water wash column cat head interface 30～40%;
2) and then with the method for the conventional distillation of band side line extraction, on same rectifying tower, take off heavily, make heavy constituent (pentane) content≤0.5% in the raw material, take off 75～85 ℃ of heavy still temperature, reflux ratio 1.5～2.5;
3) further take off gently, remove butylene, 1, light constituents such as 3 divinyl take off 55～65 ℃ of light still temperature, reflux ratio 3.5～4.5, and make the still temperature at 55～65 ℃, sensitive plate temperature under 52～62 ℃, 0.35～0.39MPa condition, extract the finished product product out from side line in a continuous manner;
Whole rectifying process is being carried out under anaerobic state, and adds an amount of stopper; Wherein:
The by product heavy constituent: it is about 5% to contain pentane, 1,3-butadiene 10～20%, and 1 5～12%, anti-butylene is about 1%, and all the other are maleic;
Side line finished product product: 1 〉=40%, pentane≤15%, anti-butylene is about 1%, and all the other are maleic;
More than be weight percent meter.
The Technology of described preparation 1 also comprises finished product product process moisture eliminator dehydrating step, makes finished product product water number≤150mg/L.
In technique scheme, the content of 1 is very important in the raw material.Preferably be controlled at 〉=7%.If 1 content is low excessively, then the 1 content in the product is difficult to reach 40%, and product is just defective.And to guarantee 1 〉=7% in the raw material, then in the extracting production process of 1,3-butadiene, the content of 1,3-butadiene in the heavy constituent of strict control by product.Requirement is controlled at≤and 25%.
Owing to contain 1～15% heavy constituent (pentane) in the raw material,, make heavy constituent content≤0.5% in the raw material so present technique requires to take off heavily rectifying earlier.And then take off light rectifying.For preventing the self-polymeric reaction of micro amount of oxygen to 1 and 1,3-butadiene, rectifying must carry out under anaerobic state, carries out under in nitrogen protection, and stopper can be used T.B.C (p-ten.-butylcatechol).
What present technique adopted is the rectifying mode of packing tower.Full tower has 8 layers of column plate, and every layer of dress liquefaction is learned and handled, and with 1% left and right sides sodium nitrite solution, goes into to set up circulation in the system with infusion, suitably is heated to about 80 ℃, circulates the micro amount of oxygen that exists in the consumption systems, paralysis facility surface about 12 hours.Every layer of column plate all has liquid phase distributor, and the gas-liquid that liquid phase distributes and tower is interior that can be beneficial to each layer column plate is mass-and heat-transfer mutually.Body of the tower adopts detachable, and every layer of column plate can be dismantled fully, so that all fillers can fully be cleaned and change, guarantees rectification effect.Filler is preferably selected for use stainless.If consider its economy, also can select the material of carbon steel for use.
The present invention can obtain qualified product 1 by above process by successive under the condition that material quantity guarantees.Its production cycle is generally about 6 months.
Problems such as the production technology that the present invention has avoided bringing because of factors such as raw material, catalyzer, by products, safety, environmental protection.Both guaranteed the production demand of 100,000 tons of/year solution styrene butadiene rubber devices, and also increased value-added content of product, its economic benefit and social benefit are all very considerable.
Embodiment
With specific embodiment the present invention is further described below.
The raw material that the present invention adopts is the last running of discharging with tower still behind the acetonitrile method extracting production divinyl.Contain wherein that pentane is about 5%, 1,3-butadiene 10～20%, 1 5～12%, anti-butylene are about 1%, all the other are maleic.
Analyze and measure:
1 concentration: vapor-phase chromatography
Trace ethane nitrile content: vapor-phase chromatography
Calculate by weight percentage
Selecting example down is to take off heavy and take off light operational condition, product result one, product index:
| Sequence number | Project | Unit | Index | Analytical procedure |
| 1 | 1 | ％ | >40.0 | Vapor-phase chromatography |
| 2 | Carbon five | ％ | <15 | Vapor-phase chromatography |
| 3 | Propadiene | ％ | <0.5 | Vapor-phase chromatography |
| 4 | Total alkynes (in vinylacetylene) | ％ | <0.5 | Vapor-phase chromatography |
| 5 | Carbonyl compound (with acetometer) | mg/kg | <15 | |
| 6 | Hydrogen sulfide | mg/kg | <15 | |
| 7 | Superoxide is (with H 20 2Meter) | mg/kg | <15 |
Two, main operational condition:
| Tower top pressure (washing) | 0.43～0.47 | Mpa |
| Tower top pressure | 0.37±0.02 | Mpa |
| Water wash column cat head interface | 30～40 | ％ |
| Inlet amount (taking off heavily) | 300～400 | Kg |
| Still temperature (taking off heavily) | 75～85 | ℃ |
| Reflux ratio (taking off heavily) | 1.5～2.5 | |
| Inlet amount (taking off light) | 190～250 | Kg |
| Sensitive plate temperature (taking off light) | 52～62 | ℃ |
| Still temperature (taking off light) | 55～65 | ℃ |
| Reflux ratio (taking off light) | 3.5～4.5 | |
| The side line produced quantity | 25～45 | Kg/h |
Three, take off the retry example:
Four, take off the light work example:
Claims (9)
1. a continuous processing prepares the Technology of styrene-butadiene rubber(SBR) inhibitor 1, and the by product reorganization of producing 1,3-butadiene with extraction process is divided into raw material, comprises the steps:
1) washing, the trace solvent of flush away remnants, washing tower top pressure 0.43～0.47Mpa, water wash column cat head interface 30～40%;
2) and then with the method for the conventional distillation of band side line extraction, on same rectifying tower, take off heavily, make pentane content≤0.5% in the raw material, take off 75～85 ℃ of heavy still temperature, reflux ratio 1.5～2.5;
3) further take off gently, remove light constituents such as butylene, 1,3-butadiene, 55～65 ℃ of still temperature, reflux ratio 3.5～4.5,
And make the still temperature at 55～65 ℃, sensitive plate temperature under 52～62 ℃, 0.35～0.39MPa condition, extract the finished product product out from side line in a continuous manner;
Whole rectifying process is carried out under anaerobic state, and adds an amount of stopper; Wherein:
The by product heavy constituent: contain pentane 5%, 1,3-butadiene 10～20%, 1 5～12%, anti-butylene 1%, all the other are maleic;
Side line finished product product: 1 〉=40%, pentane≤15%, anti-butylene 1%, all the other are maleic;
More than be weight percent meter.
2. the Technology of preparation 1 according to claim 1, its characteristics make finished product product water number≤150mg/L for also comprising finished product product process moisture eliminator dehydrating step.
3. the Technology of preparation 1 according to claim 1, its characteristics are 1 content 〉=7% in the described raw material.
4. the Technology of preparation 1 according to claim 1, its characteristics are that described rectifying carries out under nitrogen protection.
5. the Technology of preparation 1 according to claim 1, its characteristics are that the stopper that is added is a p-ten.-butylcatechol.
6. the separating device of the Technology of the described preparation 1 of claim 1 employing is a packing tower, and described packing tower has 8 layers of column plate, and every layer of dress liquid carries out chemical treatment, the paralysis facility surface, and every layer of column plate all has liquid phase distributor; The chemical treatment that described column plate adopts is to use 1% sodium nitrite solution, goes into to set up circulation in the system with infusion, suitably is heated to 80 ℃, circulates the micro amount of oxygen that exists in the consumption systems, paralysis facility surface 12 hours.
7. packing tower according to claim 6, its characteristics are stainless steel for the filler material.
8. packing tower according to claim 6, its characteristics are carbon steel for the filler material.
9. packing tower according to claim 6, its characteristics are that body of the tower is detachable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100433883A CN101337858B (en) | 2007-07-03 | 2007-07-03 | Process and equipment for preparing 1,2-butadiene by continuous method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100433883A CN101337858B (en) | 2007-07-03 | 2007-07-03 | Process and equipment for preparing 1,2-butadiene by continuous method |
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| Publication Number | Publication Date |
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| CN101337858A CN101337858A (en) | 2009-01-07 |
| CN101337858B true CN101337858B (en) | 2011-09-07 |
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| CN2007100433883A Active CN101337858B (en) | 2007-07-03 | 2007-07-03 | Process and equipment for preparing 1,2-butadiene by continuous method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504066A (en) * | 2011-11-11 | 2012-06-20 | 茂名鲁华化工有限公司 | Method for solvent refining during isoprene rubber production |
| CN103242126A (en) * | 2012-02-03 | 2013-08-14 | 青岛伊科思技术工程有限公司 | Method for producing high-purity 1,2-butadiene |
| CN104974005A (en) * | 2014-04-03 | 2015-10-14 | 中国石化工程建设有限公司 | Method for washing crude butadiene |
| CN111333480A (en) * | 2018-12-18 | 2020-06-26 | 天津普莱化工技术有限公司 | Butadiene refining method and device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175049B1 (en) * | 1998-08-27 | 2001-01-16 | Ec Erdolchemie Gmbh | Process for the production of 1, 2-butadiene |
| CN1200919C (en) * | 2002-12-31 | 2005-05-11 | 中国石化齐鲁股份有限公司 | Oxygen removing method of butadiene refining device |
-
2007
- 2007-07-03 CN CN2007100433883A patent/CN101337858B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175049B1 (en) * | 1998-08-27 | 2001-01-16 | Ec Erdolchemie Gmbh | Process for the production of 1, 2-butadiene |
| CN1200919C (en) * | 2002-12-31 | 2005-05-11 | 中国石化齐鲁股份有限公司 | Oxygen removing method of butadiene refining device |
Non-Patent Citations (1)
| Title |
|---|
| 董谊仁.《现代填料技术（二）液体分布器和再分布器》.《化工生产与技术》.1996,(第3期), * |
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