CN102329188A - Method for separating and refining high-purity 1,3-butadiene by distillation - Google Patents
Method for separating and refining high-purity 1,3-butadiene by distillation Download PDFInfo
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- CN102329188A CN102329188A CN201110220299A CN201110220299A CN102329188A CN 102329188 A CN102329188 A CN 102329188A CN 201110220299 A CN201110220299 A CN 201110220299A CN 201110220299 A CN201110220299 A CN 201110220299A CN 102329188 A CN102329188 A CN 102329188A
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Abstract
The invention discloses a technological process for separating and refining high-purity 1,3-butadiene by distillation. The method is characterized by carrying out butane/butene catalytic dehydrogenation, selective absorption and extractive distillation on the C4 fraction containing 1,3-butadiene to obtain the polymer-grade 1,3-butadiene, wherein the solvent for absorption and extractive distillation is furfural, acetonitrile or dimethyl formamide, and the ratio of raw material to solvent is 1:(10-20); the extractive distillation uses acetonitrile with the water content of 7% as the solvent to separate C4 alkanes and olefins; and the extraction column is provided with 120 column plates. The invention has the advantages of reasonable technique and simple process, and is an ideal technology for purifying 1,3-butadiene.
Description
Technical field
The present invention relates to a kind of alkanes Chemicals, particularly a kind of technology that adopts distillating method separation and purifying high-purity 1,3-butadiene is suitable for the synthetic 1,3-butadiene of chemical industry.
Background technology
C-C singly-bound internal rotation in the butadiene molecule is divided into cis and transconfiguration.The transconfiguration molecule is stable.These article are prone to liquefaction for having the colourless gas of faint aromatic odour.Fusing point-108.9 ℃, boiling point-4.41 ℃, specific density 0.6211 (20/4 ℃), zero pour-108.91 ℃, flash-point＜-6 ℃, specific refractory power 1.4292 (25 ℃), 152 ℃ of critical temperatures, emergent pressure 4326.58kPa, critical density 0.245g/cm3.Form explosive mixture, limits of explosion 2%-11.5% (vol) with air.Be dissolved in pure and mild ether, also dissolve in acetone, benzene, ethylene dichloride, amyl acetate-n and furfural, the CAA solution.Water insoluble.Easy polymerization in the presence of oxygen.Can add used as stabilizers such as a small amount of (below 1%) tert-butyl catechol, Resorcinol, mixture cresol, diarylamine based compound during storage.
Purposes: divinyl is a main raw material of producing viton (styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, X 050).Along with the development of styrene plastic(s), utilize vinylbenzene and butadiene copolymer, the production various uses is resin (like ABS resin, SBS resin, BS resin, MBS resin) widely, makes divinyl in production of resins, occupy critical role gradually.In addition, divinyl still is used to produce ENB (ethylene-propylene rubber(EPR) the 3rd monomer), 1,4-butyleneglycol (engineering plastics), adiponitrile (nylon 66 monomers), tetramethylene sulfone, anthraquinone, THF or the like.Thereby also be important basic chemical industry raw material.Divinyl also has a lot of use in fine chemicals production.With the divinyl is the fine chemicals that raw material is produced.Mainly contain the following aspects.
(1) have a liking for bifunctional vinyl compound generation Diels-Alder reaction with electron deficiency, make anthraquinone, its verivate is important dyestuff intermediate, sterilant and sterilant.
(2) with MALEIC ANHYDRIDE (abbreviation cis-butenedioic anhydride) reaction, so condensation, make THPA, can make polyester resin, curing agent for epoxy resin and softening agent.THPA can get BTCA again through nitric acid oxidation, is the raw material of making water soluble paint.Same THPA hydrogenation makes hexahydrophthalic acid anhydride, can be used as curing agent for epoxy resin.
(3) with the sulfurous gas effect, generate cyclobufene sultone, be mixed with aqueous solution hydrogenation in the presence of skeletal nickel catalyst then, make tetramethylene sulfone, be the selective solvent that aromatic hydrocarbons extraction is used.The mixture of tetramethylene sulfone and HSDB 338 can use decarbonation gas to use.
(4) the line style telomerization of divinyl is very useful in industry.Obtain eight carbon normal olefines after the line style dimerization, promptly get nonyl alcohol through hydroformylation, hydrogenation again, important use is all being arranged aspect synthetic perfume, tensio-active agent, the oil dope.Make catalyzer with cobalt complex, its dimerization, trimerization, the tetramer all are the raw materials of synthetic higher alcohols and megacyclic musk.
Original technology becomes butylene for butane dehydrogenation, and butylene dehydrogenation generates the 1,3-butadiene two-step reaction and in a reactor drum, carries out simultaneously.Reaction times is generally 5～15min, and catalyst life was generally 18～24 months, but owing to influenced by thermodynamic(al)equilibrium; Transformation efficiency is low, severe reaction conditions, regeneration, reaction; Switch frequent, the lower and butylene oxidation-dehydrogenation that grew up afterwards of the effective rate of utilization of raw material; The 1,3-butadiene in sources such as cracking by-product C 4 fraction can't be competed, so be eliminated gradually or reconstruct.
Summary of the invention
Problem to be solved by this invention is; Overcome the deficiency of prior art, disclose a kind of method that adopts distillating method separation and purifying high-purity 1,3-butadiene; It is characterized in that to contain 1; The C 4 fraction of 3-divinyl selects the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene with butane, butylene catalytic dehydrogenation; Absorption wherein and extractive distillation solvent have furfural, acetonitrile or N, and its add-on is parts by weight 1: 10-20.It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.
Adopt catalytic dehydrogenation of butanes to produce the 1,3-butadiene technical process.The butane dehydrogenation process obtains butylene and two kinds of products of 1,3-butadiene, and reaction also is a strong endothermic reaction, must and have in the presence of the catalyzer in high temperature more than 500 ℃, lower butane dividing potential drop to carry out.The temperature of reaction of butane dehydrogenation full scale plant keeps lower per pass conversion to produce the 1.3-divinyl through shortening duration of contact about 600 ℃, can not obtain highly purified 1.3-divinyl.
Present method adopts the technical process of distillating method separation and purifying high-purity 1,3-butadiene.The product that obtains with butane, butylene catalytic dehydrogenation and butylene oxidation-dehydrogenation is a kind of mixture that contains various C4 hydrocarbon, needs to adopt to select the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene.Select absorption and extractive distillation solvent that furfural, acetonitrile, N etc. are arranged.The adding of solvent has increased the relative volatility between the C4 hydrocarbon, becomes the method for separating 1,3-butadiene.
50 ℃ of following different solvents are to C
4Hydrocarbon is the influence of the relative volatility of component respectively
| C 4Hydrocarbon | Boiling point/℃ | Acetonitrile | N | N-Methyl pyrrolidone | N,N-DIMETHYLACETAMIDE | Furfural |
| Normal butane | -0.5 | 3.13 | 3.43 | 3.66 | 3.13 | 2.89 |
| 1-butylene | -6.26 | 1.92 | 2.17 | 2.38 | 2.07 | 1.78 |
| Instead-2-butylene | 0.88 | 1.59 | 1.16 | 1.90 | 1.71 | 1.20 |
| Suitable-2-butylene | 3.72 | 1.45 | 1.56 | 1.63 | 1.52 | 1.26 |
| Propine | -42.07 | 1.00 | 0.70 | 0.806 | 0.733 | 1.04 |
| 1,3-butadiene | -4.41 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| 1 | 10.85 | 0.731 | 0.72 | 0.737 | 0.714 | 0.649 |
| Ethyl acetylene | 8.7 | 0.481 | 0.424 | 0.418 | 0.439 | 0.518 |
| Vinylacetylene | 5.1 | 0.389 | 0.229 | 0.208 | 0.228 | 0.407 |
[0014]Venus crystals ammonia solution absorption process is used for butylene dehydrogenation and ethanol dehydration 1; The 1,3-butadiene of 3-divinyl process is purified, and its principle is to utilize aqueous venus crystals ammonia solution and 1; Unsaturated hydrocarbons such as 3-divinyl form complex compound; The stability of complex compound then increases with the degree of unsaturation of hydrocarbon, can tell the higher 1,3-butadiene product of purity.
The SX distillation method adopts one section or two-section extraction distillation technique usually.In the one-section abstraction still-process, at first adopt common distillatory method to tell alkynes, tell alkane and alkene through extractive distillation again, obtain the polymerization-grade 1,3-butadiene through precise distillation again.Also can in advance the C 4 fraction that contains 1,3-butadiene be carried out extractive distillation again behind selection hydrogenation and removing alkynes.Select hydrogenation process also can carry out in liquid phase in gas phase, catalyst system therefor has the palladium that is stated from aluminum oxide or the silicon oxide, cupric oxide, chromic oxide etc.In the two-section extraction still-process, at first remove butane and butene fraction through the one-section abstraction distillation.And then remove alkynes through two-stage extraction distillation, obtain the polymerization-grade 1,3-butadiene through rectifying again.Can be by separating 1,3-butadiene in the ethylene unit by-product C 4 fraction, its characteristics are for adopting one-section abstraction distillation and twice rectifying.It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.Methylacetylene and vinylacetylene are removed in rectifying, and obtaining purity is the polymerization-grade 1,3-butadiene of 99.5% (containing-α alkynes＜100 μ g/g vinylacetylene＜50 μ g/g), and the 1,3-butadiene yield of process is 96%～97%.。
Description of drawings:
Fig. 1 is for separating the 1,3-butadiene technical process; 1-evaporator tower wherein; 2-first extractive distillation column; 3-second extractive distillation column; 4-divinyl distillation tower; The 5-stripping tower; The 6-knockout tower; The 7-butadiene recovery column; The 8-cut light tower; The 9-solvent takes off the dimer tower; The 10-regenerating column; 11-tar jar; The 12-compressor; 13-dipolymer storage tank.
Embodiment:
Below in conjunction with embodiment the present invention is described; The scheme of embodiment described here; Do not limit the present invention; One of skill in the art can make improvements and change according to spirit of the present invention, and described these improvement and variation all should be regarded as within the scope of the invention, and scope of the present invention and essence are limited claim.
Embodiment 1
The C 4 fraction that will contain 1,3-butadiene selects the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene with butane, butylene catalytic dehydrogenation; Absorption wherein and extractive distillation solvent have furfural, acetonitrile or N, and its add-on is parts by weight 1: 10.Extractive distillation and twice rectifying.It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.Methylacetylene and vinylacetylene are removed in rectifying, and obtaining purity is 99.5%, and idiographic flow is seen Fig. 1.
Embodiment 2
The C 4 fraction that will contain 1,3-butadiene selects the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene with butane, butylene catalytic dehydrogenation; Absorption wherein and extractive distillation solvent have furfural, acetonitrile or N, and its add-on is parts by weight 1: 15.Extractive distillation and twice rectifying.It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.Methylacetylene and vinylacetylene are removed in rectifying, and obtaining purity is 99.5%, and idiographic flow is seen Fig. 1.
Embodiment 3
The C 4 fraction that will contain 1,3-butadiene selects the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene with butane, butylene catalytic dehydrogenation; Absorption wherein and extractive distillation solvent have furfural, acetonitrile or N, and its add-on is parts by weight 1: 20.Extractive distillation and twice rectifying.It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.Methylacetylene and vinylacetylene are removed in rectifying, and obtaining purity is 99.5%, and idiographic flow is seen Fig. 1.
Claims (1)
1. one kind is adopted distillating method to separate the method with the purifying high-purity 1,3-butadiene, it is characterized in that the C 4 fraction that contains 1,3-butadiene selecting the method for absorption, extractive distillation to obtain the polymerization-grade 1,3-butadiene with butane, butylene catalytic dehydrogenation; Absorption wherein and extractive distillation solvent have furfural, acetonitrile or N, and its add-on is parts by weight 1: 10-20; It is solvent that moisture 7% acetonitrile is adopted in extractive distillation, and extractive distillation separation of C 4 alkane and alkene, extraction tower have 120 blocks of column plates.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083516A (en) * | 2016-06-07 | 2016-11-09 | 安徽泰合森能源科技有限责任公司 | Use the method for 1,3 butadiene in extracting rectifying removing alkylate oil raw materials for production |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083516A (en) * | 2016-06-07 | 2016-11-09 | 安徽泰合森能源科技有限责任公司 | Use the method for 1,3 butadiene in extracting rectifying removing alkylate oil raw materials for production |
| CN106083516B (en) * | 2016-06-07 | 2018-09-18 | 安徽泰合森能源科技有限责任公司 | The method that 1,3- butadiene in alkylate oil raw materials for production is removed using extracting rectifying |
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Application publication date: 20120125 |