CN102091498A - Method for treating tail gas produced by terephthalic acid - Google Patents
Method for treating tail gas produced by terephthalic acid Download PDFInfo
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- CN102091498A CN102091498A CN2009102586810A CN200910258681A CN102091498A CN 102091498 A CN102091498 A CN 102091498A CN 2009102586810 A CN2009102586810 A CN 2009102586810A CN 200910258681 A CN200910258681 A CN 200910258681A CN 102091498 A CN102091498 A CN 102091498A
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- Prior art keywords
- ionic liquid
- tail gas
- gas stream
- down group
- terephthalic acid
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Abstract
The invention relates to a method for removing impurities from a tail gas flow in the production process of terephthalic acid. The tail gas flow is in contact with ionic liquid and adsorbs impurities from air. The method can adopt single bed layer or a plurality of bed layers in the pressure swing adsorption process.
Description
Background technology
Terephthalic acid (TPA) usually by paraxylene the carboxylic acid solvent, in acetic acid, in the presence of the heavy metal catalyst system, make through peroxidization.Also adopt a kind of bromine component to be used as co-catalyst.This oxidation reaction is strong heat release, and the heat of generation makes some the liquid evaporations in the oxidation reactor.And about 2% to 7% the acetate solvate that joins in the oxidation reactor is degraded into methyl alcohol and oxycarbide.Therefore, in the tail gas of oxidation reaction (orr-gas), typically contain a large amount of acetic acid, water and nitrogen, and a spot of oxygen, oxycarbide comprises carbon dioxide and carbon monoxide, the organic compound that also has other, as paraxylene, benzene, toluene, methyl acetate, other bromide of bromomethane and trace.
In the conventional technical process, be earlier by a condenser system from the processing of the logistics at oxidation reactor top, partial condensation liquid turns back in the reactor and goes.Owing to there is water to exist, so a part of condensate liquid is sent to separative element, destilling tower typically, with water and solvent, acetic acid separated so that in the reactor concentration keep constant level.The uncooled gas that gets off from the condenser system top enters the high pressure scrubbing tower, by further reclaiming acetic acid with acetic acid or water counter current contacting.The acetic acid that obtains at the bottom of the scrubbing tower and the mixture of water are supplied with destilling tower usually, and the rich acetic acid product at the bottom of a part of tower is also turned back in the reactor.Methyl acetate reclaims by distillation or by multistage distillation be arranged on the method that catalytic conversion process on the cationic ion-exchange resin in the acetic acid dehydrating tower changes into acetic acid and methyl alcohol and reclaim.
The pressure from the oxidation reaction tail gas of scrubbing tower that produces in the paraxylene technology of routine based on air is 10 to 16 crust, and temperature is about 40 ℃.Its composition with what molar fraction was represented is: 94.5% nitrogen, and 3.0% oxygen, 0.45% carbon monoxide, 1.35% carbon dioxide, 0.5% water and 0.2% organic matter, this organic matter comprises acetic acid, methyl acetate, methyl alcohol, benzene, toluene, paraxylene and bromomethane.Adopt oxygen-enriched air can improve the concentration of organic compound in the tail gas stream as oxidant.
Bromomethane is poisonous, if discharge into the atmosphere, it is reported that meeting consumes the ozone in the atmosphere.As awaiting the reply disclosed in patent application PCT/IB/2008/000777 of common transfer, bromomethane loops back oxidation reactor, the mordant bromomethane that is accumulated in the system then requires equipment and materials to have corrosion resistance more than conventional Production of Terephthalic Acid system, and also may bring influence to product quality.
The technology of early stage processing oxidation reaction tail gas includes the catalytic combustion of organic compounds, and the expansion by gas turbine recovers energy, and adopts alkaline solution washing carrying out debrominate before in being disposed to atmosphere.Alternatively, load the adsorbent bed of active carbon and silica gel from the tail gas employing of high pressure scrubbing tower and handled, adopted gas turbine to recover energy then.The waste gas that adsorption bed regeneration the time is produced adopt catalytic combustion the method processing with allow compliance with emission standards.But, in exhaust treatment system, increase the catalytic combustion unit of the fixed bed comprise the platinum that is supported on the inert carrier and/or palladium catalyst usually, make cost of investment increase about 10%.Therefore, in the Production of Terephthalic Acid process, need effectively oxidation reaction exhaust gas treating method cheaply.
Summary of the invention
The invention provides the method that adopts ionic liquid to handle the tail gas that produces in the Production of Terephthalic Acid process.When tail gas contacted with ionic liquid, ionic liquid adsorbed impurity from tail gas.
The invention provides the method that purifies the tail gas that the Production of Terephthalic Acid process produces, this method comprises tail gas stream sent into and contains ion liquid container.
The impurity that exists in the tail gas that the Production of Terephthalic Acid process produces is selected from group down: alkyl bromide compound, carbon dioxide, carbon monoxide and other organic component.
In another embodiment, the invention provides a kind of method of from the impure tail gas that the Production of Terephthalic Acid process produces, removing impurity, may further comprise the steps:
A) described tail gas stream is sent into contained ion liquid first contactor, wherein, from tail gas stream, remove impurity;
B) a described tail gas stream part is free from foreign meter imports second contactor, and wherein, tail gas stream free from foreign meter makes the ionic liquid regeneration that is present in second contactor; With
C) tail gas stream free from foreign meter with remainder imports the recovery unit.
This embodiment can be that one way is one-pass, perhaps can be circulating, makes that second container regenerated when a container is adsorbing impurity in the feed gas stream.
Ionic liquid is the salts substances of ion fully, in very wide temperature range, is liquid in-96 ℃ to 200 ℃ scopes usually.Ionic liquid also is nonvolatile, can come special by cation and anionic combination preferably.
In one aspect of the invention, preferred ionic liquid is selected from down group: based on imidazoline, and pyridine, pyrrolin, guanidine, ammonium, phosphorus, the ionic liquid of sulfone (sulphonium), perhaps their mixture.These ionic liquids are ionic liquids (TSIL) of particular task.These ionic liquids have following structure:
Cation
Anion
Deng.
Be denoted as R
1, R
2, R
3, and R
4Various group be different alkyl and thiazolinyls.These groups can be selected from down group: hydrogen, and the straight or branched alkyl and the thiazolinyl that contain 1 to 12 carbon atom.Some amine groups, as in thiocarbamide or the amino cation that also can be combined in the ionic liquid to improve chelating CO
2Ability.In addition, hydroxyl also can be combined on the cation.For an application-specific, need to consider cation and anion optimum organization are got up with the adsorption capacity of realization ionic liquid height and high heat endurance.
The present invention has following advantage with respect to the tail gas treatment process in other the Production of Terephthalic Acid process: efficient is higher, this be since ionic liquid to carbon dioxide, carbon monoxide, the high cause of solubility of the organic compounds that alkyl bromide and other are harmful; Be used to remove the anchored in place of these impurity and the integrated process of conversion; The separative element volume is little, so cost of investment is low; Needn't catalytic combustion unit, only regenerate a spot of ionic liquid but not the big adsorbent bed of regenerating are so running cost is low.
Detailed description of the present invention
Ionic liquid of the present invention is selected from down group: imidazolinyl, and pyridine radicals, pyrrolinyl, guanidine radicals, ammonium, the phosphorus base, with the ionic liquid of sulfuryl, perhaps their mixture.These ionic liquids are ionic liquids (TSIL) of particular task.These ionic liquids have following structure:
Cation
Anion
Be denoted as R
1, R
2, R
3And R
4Various group be different alkyl and thiazolinyls.These groups can be selected from hydrogen, and the straight or branched alkyl and the thiazolinyl that contain 1 to 12 carbon atom.Some amine groups also can be combined on the ion liquid cation to improve chelating CO as thiocarbamide or amino
2Ability.In addition, hydroxyl also can be combined on the cation.For a special application-specific, need to consider cation and anion optimum organization are got up with the adsorption capacity of realization ionic liquid height and high heat endurance.
Ionic liquid can be coated on the surface of base material, base material is added in the bed that feeds tail gas to be clean.
Ionic liquid also can be by applying or sealing on porous bead and/or the pill and use.The bead that applied and/or pill can be packed in the container, can be fixed bed, the form of moving bed or fluid bed.
Also ionic liquid can be applied or seals the bead and/or the pill of porous, these beads and/or pill can be fixed to or be impregnated in the sheet material of stacked or lamination.Include the bead that applied and/or the coated sheet of pill and use, in the time of in being stacked on container, leave the gap between each sheet by the mode that is stacked.Gas flow direction to be clean is parallel with sheet surface.When employing included multichannel porous bead and/or pill in adsorbent bed, the resistance of gas flow can be similar in all directions.Under these situations gas flow may with individual other bead and/or ball-shape at an angle, but can be subjected to the influence of adsorbent bed engineering design.In the application that is used for as packed bed, gas flow or along bed axially, or in radial bed absorber situation along radially.
If ionic liquid material is coated on the monolithic substrate, the flow direction of gas by the block base material adsorbent of monoblock type is parallel to the passage in the block base material of monoblock type, so that the pressure drop minimum.In some cases, the made of one piece sorbent material has the passage that is parallel to each other in one direction, and gas flow direction is only in the channel direction that is parallel in sorbent material.
Ionic liquid can functionalised, and makes chemical group to be joined in the ionic liquid structure to go, and gives ionic liquid other behaviour.
Can utilize the ionic liquid of a series of particular task among the present invention.These ionic liquids can be modified to improve the ability of carbon dioxide, bromomethane class and other harmful organic compound in the chelating Production of Terephthalic Acid process tail gas.By to ion liquid cation and anionic modification and/or in conjunction with the rate of adsorption and the adsorption capacity that improve these components.Amino acid 4-butyl-phosphonium class ionic liquid shows the carbon dioxide high absorption capacity.
By catalyst junction being incorporated into the carbon monoxide that goes in the ionic liquid can to realize removing in the tail gas.The group that giving ionic liquid has catalytic activity can make the effect of ionic liquid performance catalyst, perhaps as the solvent of catalyst..For carbon monoxide is transformed, catalyst includes but not limited to and noble metal, as platinum, and the combination of palladium and rhodium.The oxidant that is used for the carbon monoxide conversion can be the oxygen of feeding air, is dissolved in the oxidant in ionic liquid or the custom-designed ionic liquid, as H
2O
2, NaClO etc.
When in the tail gas stream water being arranged, tail gas with can adopt a drying unit before ionic liquid contacts.This drying unit can be an adsorbent bed that is filled with activated alumina.
The component of being caught by ionic liquid, as oxycarbide, alkyl bromide class and other harmful organic compound can utilize ionic liquid as reaction dissolvent, catalyst or co-catalyst and change into harmless or valuable product.For example, can adopt the technology that the original position combination is fixed-transformed in ionic liquid.
The bromomethane of chelating can be removed at the ionic liquid regeneration period, perhaps removes by changing into hydrogen bromide.In order to transform the alkyl bromide compound, catalyst includes but not limited to promote the catalyst material of hydrolysis or promotion hydrogenation reaction as used herein.The product that forms in alkyl bromide hydrolysis/hydrogenation process comprises hydrogen bromide and corresponding alcohols/hydro carbons.Separating of hydrogen bromide and alcohols/hydro carbons can realize simultaneously.Can be with in the hydrogen bromide Returning oxidation reactor that reclaims.
Ionic liquid of the present invention can be used for single bed system or has in the two or more system.When adopting multibed system, this system can be circulating, and when making the impurity of a bed in the absorption feed gas stream, another bed is then being regenerated.
Ionic liquid can be a single ionic liquid, or the different kinds of ions mixtures of liquids, can also combine with them as the solvent material of other functional compounds.
Ionic liquid can be used for the adsorbent bed of various systems.Ionic liquid can be used for transformation absorption (PSA), alternating temperature absorption (TSA), become vacuum suction (vacuum swing adsorption) (VSA), Vacuum Pressure Swing Adsorption (vacuum pressure swing adsorption) is (in (VPSA) and degree of thickening absorption (CSA) process.
Typical PSA circulation comprises following sequential steps: pressurize, discharge desorption, equalization of pressure and purging under (product withdrawal) absorption, venting, the lower pressure with product.
Although described the present invention with regard to special embodiment, obviously, many other form and the distortion of the present invention are conspicuous for the professional person of those industry.Claims of the present invention should be considered to cover all so conspicuous form and distortion, and they are within practicalness of the present invention and scope.
Claims (19)
1. method that purifies Production of Terephthalic Acid process tail gas, this method comprise tail gas stream sent into and contain ion liquid container.
2. the method for claim 1 is characterized in that, described ionic liquid is selected from down group: based on the ionic liquid of imidazoline, pyridine, pyrrolin, guanidine, ammonium, phosphorus, sulfone, and perhaps their mixture.
3. method as claimed in claim 2 is characterized in that, described ionic liquid has following structure:
Cation
Anion
In the formula, R
1, R
2, R
3And R
4Be different alkyl and thiazolinyls, be selected from down group: hydrogen, contain the straight or branched alkyl and the thiazolinyl of 1-12 carbon atom.
4. method as claimed in claim 3, this method further comprise the amine that is selected from thiocarbamide and amino that is present in the described ionic liquid.
5. method as claimed in claim 3, this method further comprises the hydroxyl that is attached on the described cation.
6. the method for claim 1 is characterized in that, described impurity is selected from down group: alkyl bromide compound, carbon dioxide and carbon monoxide.
7. the method for claim 1 is characterized in that, described ionic liquid is coated on the surface of base material.
8. the method for claim 1 is characterized in that, described ionic liquid is applied or is encapsulated on porous bead and the pill.
9. method of from the impure tail gas of Production of Terephthalic Acid process, removing impurity, this method may further comprise the steps:
A) described tail gas stream importing is contained ion liquid first contactor, wherein, from tail gas stream, remove impurity;
B) described tail gas stream that a part is free from foreign meter is sent into and is contained ion liquid second contactor, and wherein, tail gas stream free from foreign meter will be regenerated at the ionic liquid in second contactor; With
C) tail gas stream free from foreign meter with remainder imports the recovery unit.
10. method as claimed in claim 9, it is characterized in that, the impure tail gas of described Production of Terephthalic Acid process is sent into described second adsorbent bed, and the described tail gas stream that a part is free from foreign meter is sent into and is contained ion liquid first contactor, makes described first contactor regeneration.
11. method as claimed in claim 9 is characterized in that, described ionic liquid is selected from down group: based on the ionic liquid of imidazoline, pyridine, pyrrolin, guanidine, ammonium, phosphorus, sulfone, and perhaps their mixture.
12. method as claimed in claim 11 is characterized in that, described ionic liquid has following structure:
Cation
Anion
In the formula, R
1, R
2, R
3And R
4Be different alkyl and thiazolinyls, be selected from down group: hydrogen, contain the straight or branched alkyl and the thiazolinyl of 1-12 carbon atom.
13. method as claimed in claim 11, this method further comprise the amine that is selected from thiocarbamide and amino that is present in the described ionic liquid.
14. method as claimed in claim 11, this method further comprises the hydroxyl that is combined on the described cation.
15. method as claimed in claim 9 is characterized in that, described impurity is selected from down group: alkyl bromide compound, carbon dioxide and carbon monoxide.
16. method as claimed in claim 11 is characterized in that, described ionic liquid is coated on the surface of base material.
17. method as claimed in claim 11 is characterized in that, described ionic liquid is applied or is encapsulated on porous bead and the pill.
18. method as claimed in claim 11 is characterized in that, described method is selected from down group: transformation absorption, alternating temperature absorption becomes vacuum suction, Vacuum Pressure Swing Adsorption and degree of thickening adsorption method.
19. method as claimed in claim 18 is characterized in that, described method is cycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910258681.0A CN102091498B (en) | 2009-12-14 | 2009-12-14 | Method for treating tail gas produced by terephthalic acid |
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|---|---|---|---|
| CN200910258681.0A CN102091498B (en) | 2009-12-14 | 2009-12-14 | Method for treating tail gas produced by terephthalic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989262A (en) * | 2011-09-09 | 2013-03-27 | 岩谷产业株式会社 | Method and apparatus for concentrating ozone gas |
| CN106178835A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of methylarenes liquid phase oxidation esterification technology for absorbing tail gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005009393A1 (en) * | 2005-03-01 | 2006-09-14 | Linde Ag | Process for adsorber regeneration |
| CN101032677A (en) * | 2006-03-08 | 2007-09-12 | 波克股份有限公司 | Method of gas purification |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989262A (en) * | 2011-09-09 | 2013-03-27 | 岩谷产业株式会社 | Method and apparatus for concentrating ozone gas |
| CN102989262B (en) * | 2011-09-09 | 2017-03-01 | 岩谷产业株式会社 | Ozone gas method for concentration |
| CN106178835A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of methylarenes liquid phase oxidation esterification technology for absorbing tail gas |
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| CN102091498B (en) | 2015-07-01 |
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