CN203269815U - Production apparatus for preparing isobutene by using absorption separation method - Google Patents
Production apparatus for preparing isobutene by using absorption separation method Download PDFInfo
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- CN203269815U CN203269815U CN 201220745136 CN201220745136U CN203269815U CN 203269815 U CN203269815 U CN 203269815U CN 201220745136 CN201220745136 CN 201220745136 CN 201220745136 U CN201220745136 U CN 201220745136U CN 203269815 U CN203269815 U CN 203269815U
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- butylene
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- normal hexane
- butene
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Abstract
The utility model discloses an apparatus for preparing isobutene by using an absorption separation method. The apparatus is characterized by comprising a hydrogenation reactor 1, an absorption bed 2, a n-hexane storage tank 3, a separation tower (isobutene/n-hexane) 4, an isobutene rectification tower 5, a n-hexane purification tower 6, a separation tower (n-butene, n-hexane) 7, a n-butene rectification tower 8, a material inlet 9, 2-butene and n-butane 10, an oligomer 11, 1-butene 12, isobutene 13, and isobutane 14. The production apparatus has characteristics of reasonable process and simple production, and is the easiest ideal isobutene preparation technology.
Description
Technical field
The utility model relates to the technology of a kind of Chemicals, particularly a kind of preparing isobutylene by adsorption separation, is suitable for producing iso-butylene.
Background technology
(CH3) 2C=CH
2Claim again the 2-methacrylic.Inflammable, explosion hazard gases (limits of explosion 1.7%～9.0% volume), boiling point-6.90 ° C, 144.75 ° of C of critical temperature, emergent pressure 4.00MPa.Industrial, iso-butylene is nearly all by obtaining in refinery gas and c4 cleavage cut (seeing C-4-fraction).In refinery gas, the content of iso-butylene is generally 5%～12%, is generally 20%～30% in the c4 cleavage cut.Made by catalytic dehydrogenation of isobutane with chromic oxide-on-alumina catalyst under a few cases.When producing propylene oxide take propylene and Trimethylmethane as raw material with conjugated oxidation, iso-butylene is its co-product.By the C-4-fraction isobutylene separation, tell formerly normally that wherein divinyl carries out later on.The most frequently used isobutylene separation device is sulfuric acid absorption method, gained iso-butylene purity〉99%, the rate of recovery reaches 92%.Molecular sieve adsorption, the molecular sieve of employing certain pore size scope (approximately 3～10 ┱) is optionally isolated butylene and normal butane from the C 4 fraction raffinate, and gained iso-butylene purity reaches 99%.Ion-exchange-resin process also can get high-purity isobutylene, but because reaction efficiency is low, uses wideless.In addition, also have take Zeo-karb as catalyzer, generate methyl tertiary butyl ether with isobutene reaction in methyl alcohol and C 4 fraction, and the trimer that isobutene oligomerisation is generated diisobutylene and iso-butylene under an acidic catalyst effect, thereby the device such as separate with other components in the C 4 fraction raffinate.Methyl tertiary butyl ether method more promising (seeing that C-4-fraction separates).Industrial high density iso-butylene is mainly for the production of polyisobutene and and isoprene copolymer production isoprene-isobutylene rubber.Iso-butylene and Trimethylmethane carry out alkylated reaction, can produce the high-octane rating gasoline alkylate, with methyl alcohol reaction gained methyl tertiary butyl ether be good gasoline dope, oligomerisation gained dipolymer and trimer are the additive of vaporizer fuel after hydrogenation, also are applicable to do the raw material for alkylation of aromatic hydrocarbons.Diisobutylene also can be used as the raw material production isononyl alcohol of oxo process, further makes softening agent.In addition, iso-butylene can get methacrylic acid through oxidation, gets methacrylonitrile through ammoxidation, the rehydrated trimethyl carbinol that makes.
Summary of the invention
problem to be solved in the utility model is, overcomes the deficiencies in the prior art, and a kind of device of preparing isobutylene by adsorption separation is provided, and it is characterized in that comprising the 1-hydrogenator, the 2-adsorption bed, 3-normal hexane basin, 4-knockout tower (iso-butylene/normal hexane), 5-iso-butylene rectifying tower, 6-normal hexane scavenging tower, 7-knockout tower (n-butene, normal hexane), 8-n-butene rectifying tower, the 9-opening for feed, 10-2-butylene and normal butane, the 11-oligopolymer, the 12-1-butylene, the 13-iso-butylene, the 14-Trimethylmethane, after being passed into 1 hydrogenator that 9 opening for feeds rinse with normal hexane in advance, the C4 material of having vaporized enters 2 adsorption beds, the adsorption of carrying out on the one hand n-butene enters into 7 knockout towers, normal hexane and n-butene after desorption are discharged by tower top, 11 oligopolymer enter into 8 n-butene rectifying tower n-butene is separated after, discharge the 12-1-butylene from upper tower, lower tower is discharged 10-2-butylene and normal butane, normal hexane carries out recycle in 7 knockout towers return to 3 normal hexane tank systems, desorption from 2-adsorption bed desorb generation normal hexane enters 4 knockout towers on the other hand, the heavy constituent normal hexane enters 3 normal hexane storage tanks and recycles, light constituent enters into 5 iso-butylene rectifying tower, extract 14 Trimethylmethanes in upper tower, extract 13 iso-butylenes in lower tower.
Original technology is that isopropylcarbinol is at 360 ~ 370 ℃, can get 86% ~ 87% thick iso-butylene 0.304 carry out dehydration reaction (catalyzer is activated alumina) under ~ 0.405MPa(3 ~ 4atm), then can make with extra care iso-butylene through rectifying and after except acetaldehyde, ether, organic acid, original device reaction temperature is high, energy consumption is high, and product is single.The utility model discloses a kind of technology of preparing isobutylene by adsorption separation, substantially do not contain iso-butylene in Sweet natural gas, oil field gas and crude oil, a large amount of iso-butylenes wherein contains iso-butylene in the C 4 fraction with catalytic cracking unit by-product in the refinery maximum mainly from refinery gas and petrochemical complex gas.Following table is that some typical refinery gass form.
Refinery gas composition/% (massfraction)
| Project | Air distillation | Catalytic cracking | Catalytic reforming | Hydrocracking | Hydrofining | Delayed coking | Viscosity breaking |
| H 2 | - | 0.6 | 1.5 | 1.4 | 3.0 | 0.6 | 0.3 |
| CH 4 | 8.5 | 7.9 | 6.0 | 21.8 | 24.0 | 23.3 | 8.1 |
| C 2H 6 | 15.4 | 11.5 | 17.5 | 4.4 | 70.0 | 15.8 | 6.8 |
| C 2H 4 | - | 3.6 | - | - | - | 2.7 | 1.5 |
| C 3H 8 | 30.2 | 14.0 | 31.5 | 15.3 | 3.0 | 18.1 | 8.6 |
| C 3H 6 | - | 16.9 | - | - | - | 6.9 | 4.8 |
| C 4H 10 | 45.9 | 21.3 | 43.5 | 57.1 | - | 18.8 | 36.4 |
| C 4H 8 | - | 24.2 | - | - | - | 13.8 | 33.5 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
In petrochemical process, produce as hydrocarbon cracking in the technological process of ethene, also there is a certain amount of iso-butylene to generate, but comparatively small amt generally is not separated into pure component, and together with other C4 hydro carbons, or return as the raw material of cracking of ethylene, or dispatch from the factory as product (liquefied gas).The iso-butylene of these by-products is all to mix with other C4 components, forms C 4 fraction.The iso-butylene that obtains higher degree need to be taked some special tripping devices.Adopt general rectifier unit just the hydro carbons of C4 hydro carbons with other carbon numbers can be separated, but will obtain highly purified iso-butylene from the hybrid C 4 hydro carbons need to separate according to the composition of hybrid C 4 hydro carbons.Following table is the boiling point of C4 hydro carbons, can see that the boiling point between them is very approaching from table, and especially 1-butylene and iso-butylene only differ from 0.6 ℃, are not that general rectifier unit can separate.
The boiling point of various C4 hydro carbons
| The hydro carbons title | Boiling point/K | Boiling point/℃ | The hydro carbons title | Boiling point/K | Boiling point/℃ |
| Trimethylmethane | 261.42 | -11.73 | Cis-2-butene | 276.85 | 3.7 |
| Normal butane | 272.65 | -0.5 | Trans-2-butene | 274.05 | 0.9 |
| Iso-butylene | 266.25 | -6.9 | 1,3-butadiene | 268.74 | -4.41 |
| 1-butylene | 266.85 | -6.3 | 1，2-butadiene | 284.00 | 10.85 |
Iso-butylene also can be under the existence of hydrogen, with the device acquisition of acetylene polymerization.Dehydrogenation of isobutane also can obtain iso-butylene.In addition, or isopropylcarbinol dehydration synthetic from carbon monoxide and hydrogen all can obtain iso-butylene.
The utility model technology is the adsorbent of molecular sieve that highly selective will be arranged, the absorption method isobutylene separation.This method sorbent material used is the 5A molecular sieve with the calcium modification, adopts multistage bed absorption method.In order to make sorbent material can process continuously the C4 material, require to have three fixed-bed adsorbers at least, an absorption namely to be arranged simultaneously, the reactor of desorption and a regeneration (burning).Because adsorbent surface has acidity, easily make alkene generation polymerization, thus the inhibition measure should be arranged, such as adding stopper and preventing high-temperature operation etc.In addition, why without the water vapour desorption, and adopt normal hexane, heptane etc. as desorbing agent in operating process, its reason also is this.This law adopts vapor phase process, and the adsorption and desorption process is all carried out under 100 ℃ and 101.325kPa pressure.Adsorption liquid is carried out rectifying, to remove a small amount of normal butane and 2-butylene, last gained 1-butylene purity＞99.0%.The C4 material of having vaporized is passed in advance in the first adsorption tower that rinses with normal hexane, and produce on the one hand the desorption of normal hexane this moment, carries out on the other hand the adsorption of n-butene.Normal hexane and iso-butylene after desorption are discharged by tower top, after iso-butylene is separated, carry out recycle in the normal hexane retrieval system.
Description of drawings:
Fig. 1 is the preparing isobutylene by adsorption separation schema; The 1-hydrogenator; The 2-adsorption bed; 3-normal hexane basin; 4-knockout tower (iso-butylene/normal hexane); 5-iso-butylene rectifying tower; 6-normal hexane scavenging tower; 7-knockout tower (n-butene, normal hexane); 8-n-butene rectifying tower; The 9-opening for feed; 10-2-butylene and normal butane; The 11-oligopolymer; The 12-1-butylene; The 13-iso-butylene; The 14-Trimethylmethane.
Embodiment:
Below in conjunction with embodiment, the utility model is described, the scheme of embodiment described here, do not limit the utility model, one of skill in the art can make improvements and change according to spirit of the present utility model, described these improvement and variation all should be considered as in scope of the present utility model, and scope of the present utility model and essence are limited by claim.
Embodiment 1
a kind of device of preparing isobutylene by adsorption separation is characterized in that comprising the 1-hydrogenator, the 2-adsorption bed, 3-normal hexane basin, 4-knockout tower (iso-butylene/normal hexane), 5-iso-butylene rectifying tower, 6-normal hexane scavenging tower, 7-knockout tower (n-butene, normal hexane), 8-n-butene rectifying tower, the 9-opening for feed, 10-2-butylene and normal butane, the 11-oligopolymer, the 12-1-butylene, the 13-iso-butylene, the 14-Trimethylmethane, after being passed into 1 hydrogenator that 9 opening for feeds rinse with normal hexane in advance, the C4 material of having vaporized enters 2 adsorption beds, the adsorption of carrying out on the one hand n-butene enters into 7 knockout towers, normal hexane and n-butene after desorption are discharged by tower top, 11 oligopolymer enter into 8 n-butene rectifying tower n-butene is separated after, discharge the 12-1-butylene from upper tower, lower tower is discharged 10-2-butylene and normal butane, normal hexane carries out recycle in 7 knockout towers return to 3 normal hexane tank systems, desorption from 2-adsorption bed desorb generation normal hexane enters 4 knockout towers on the other hand, the heavy constituent normal hexane enters 3 normal hexane storage tanks and recycles, light constituent enters into 5 iso-butylene rectifying tower, extract 14 Trimethylmethanes in upper tower, extract 13 iso-butylenes in lower tower.
Embodiment 2
With the 5A molecular sieve of calcium modification, adopt multistage bed absorption method.In order to make sorbent material can process continuously the C4 material, three fixed-bed adsorbers are arranged, an absorption, the reactor of a desorption and a regeneration namely will be arranged simultaneously; The adsorption and desorption process is all carried out under 100 ℃ and 101.325kPa pressure.Adsorption liquid is carried out rectifying, to remove a small amount of normal butane and 2-butylene, last gained 1-butylene purity＞99.0%; The C4 material of having vaporized is passed in advance in the first adsorption tower that rinses with normal hexane, and produce on the one hand the desorption of normal hexane this moment, carries out on the other hand the adsorption of n-butene; Normal hexane and iso-butylene after desorption are discharged by tower top, after iso-butylene is separated, carry out recycle in the normal hexane retrieval system, specifically see schema 1.
Claims (1)
1. the device of a preparing isobutylene by adsorption separation, is characterized in that comprising hydrogenator (1), adsorption bed (2), normal hexane basin (3), iso-butylene/normal hexane knockout tower (4), iso-butylene rectifying tower (5), normal hexane scavenging tower (6), n-butene/normal hexane knockout tower (7), n-butene rectifying tower (8), opening for feed (9), 2-butylene and normal butane (10) oligopolymer (11), 1-butylene (12), iso-butylene (13), Trimethylmethane (14), the C4 material of having vaporized is passed into opening for feed (9), in advance after the hydrogenator (1) with the normal hexane flushing, enter adsorption bed (2), the adsorption of carrying out on the one hand n-butene enters into knockout tower (7), normal hexane and n-butene after desorption are discharged by tower top, oligopolymer (11) enters into n-butene rectifying tower (8), after n-butene is separated, discharge 1-butylene (12) from upper tower, lower tower is discharged 2-butylene and normal butane (10), normal hexane self-separation tower (7) returns in normal hexane storage tank (3) system and carries out recycle, desorption from adsorption bed (2) desorb generation normal hexane enters knockout tower (4) on the other hand, the heavy constituent normal hexane enters normal hexane storage tank (3) and recycles, light constituent enters into iso-butylene rectifying tower (5), extract Trimethylmethane (14) in upper tower, extract iso-butylene (13) in lower tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201220745136 CN203269815U (en) | 2012-12-31 | 2012-12-31 | Production apparatus for preparing isobutene by using absorption separation method |
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| CN 201220745136 CN203269815U (en) | 2012-12-31 | 2012-12-31 | Production apparatus for preparing isobutene by using absorption separation method |
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| CN203269815U true CN203269815U (en) | 2013-11-06 |
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| CN 201220745136 Expired - Fee Related CN203269815U (en) | 2012-12-31 | 2012-12-31 | Production apparatus for preparing isobutene by using absorption separation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187664A (en) * | 2016-07-05 | 2016-12-07 | 中石化上海工程有限公司 | The method preparing isobutene. |
| CN113474317A (en) * | 2018-12-18 | 2021-10-01 | 沙特基础工业全球技术公司 | Separation of olefinic components from mixtures of butanes and butenes using rectification and adsorbents |
-
2012
- 2012-12-31 CN CN 201220745136 patent/CN203269815U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187664A (en) * | 2016-07-05 | 2016-12-07 | 中石化上海工程有限公司 | The method preparing isobutene. |
| CN106187664B (en) * | 2016-07-05 | 2018-12-04 | 中石化上海工程有限公司 | The method for preparing isobutene |
| CN113474317A (en) * | 2018-12-18 | 2021-10-01 | 沙特基础工业全球技术公司 | Separation of olefinic components from mixtures of butanes and butenes using rectification and adsorbents |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131106 Termination date: 20141231 |
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| EXPY | Termination of patent right or utility model |