CN102091498B - 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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- CN102091498B CN102091498B CN200910258681.0A CN200910258681A CN102091498B CN 102091498 B CN102091498 B CN 102091498B CN 200910258681 A CN200910258681 A CN 200910258681A CN 102091498 B CN102091498 B CN 102091498B
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- ionic liquid
- tail gas
- gas stream
- thiazolinyl
- contactor
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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 carboxylic acid solvent, as in acetic acid, under the existence of heavy metal catalyst system, obtain through peroxidization.A kind of bromine component is also adopted to be used as co-catalyst.This oxidation reaction is strong heat release, and the heat of generation makes some liquid in oxidation reactor evaporate.And the acetate solvate joined in oxidation reactor of about 2% to 7% is degraded into methyl alcohol and oxycarbide.Therefore, in the tail gas (orr-gas) of oxidation reaction, typically containing a large amount of acetic acid, water and nitrogen, and a small amount of oxygen, oxycarbide, comprises carbon dioxide and carbon monoxide, also has other organic compound, as paraxylene, benzene, toluene, methyl acetate, other bromide of bromomethane and trace.
In conventional technical process, the process from the logistics at oxidation reactor top is that partial condensation liquid turns back in reactor and goes first by a condenser system.Owing to there being water to exist, so a part of condensate liquid is sent to separative element, destilling tower typically, by water and solvent, the level that acetic acid separated keeps constant to make concentration in reactor.The uncooled gas got off from condenser system top enters high pressure scrubbing tower, by with acetic acid or the further recovery of acetic acid of water counter current contacting.The acetic acid obtained at the bottom of scrubbing tower and the mixture of water supply destilling tower usually, the rich acetic acid product at the bottom of a part of tower are also turned back in reactor.Methyl acetate reclaims by Distillation recovery or by multistage distillation and catalytic conversion process changes into acetic acid and methyl alcohol on being arranged in acetic acid dehydrating tower cationic ion-exchange resin method.
The pressure of the oxidation reaction tail gas from scrubbing tower produced in the paraxylene technique of routine based on air is 10 to 16 bar, and temperature is about 40 DEG C.What its composition represented with molar fraction is: 94.5% nitrogen, 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 tail gas stream as oxidant.
Bromomethane is poisonous, if discharged into the atmosphere, it is reported the ozone that can consume in air.As disclosed in the co-pending patent application PCT/IB/2008/000777 that jointly transfers the possession of, bromomethane loops back oxidation reactor, accumulation mordant bromomethane in systems in which then requires that equipment and materials has corrosion resistance more than conventional Production of Terephthalic Acid system, and also may bring impact to product quality.
The technique of early stage process oxidation reaction tail gas includes the catalytic combustion of organic compounds, is recovered energy by the expansion of gas turbine, and before being disposed in air, adopt alkaline wash to carry out debrominate.Alternatively, the tail gas from high pressure scrubbing tower adopts the adsorbent bed having loaded active carbon and silica gel to process, and then adopts gas turbine to recover energy.During adsorption bed regeneration the waste gas that produces adopt the method process of catalytic combustion to meet discharge standard.But, in exhaust treatment system, increase the catalytic combustion unit of the fixed bed usually comprising platinum and/or the palladium catalyst supported on a inert carrier, make cost of investment increase about 10%.Therefore, need effective in Production of Terephthalic Acid process, low cost oxidation reaction exhaust gas treating method.
summary of the invention
The invention provides and adopt ionic liquid to process the method for the tail gas produced in Production of Terephthalic Acid process.When tail gas contacts with ionic liquid, ionic liquid is adsorbing contaminant from tail gas.
The invention provides the method for the tail gas that purification Production of Terephthalic Acid process produces, the method comprises sends tail gas stream into the container containing ionic liquid.
The impurity existed in the tail gas that Production of Terephthalic Acid process produces is selected from lower group: alkyl bromide compound, carbon dioxide, carbon monoxide and other organic component.
In another embodiment, the invention provides a kind of from Production of Terephthalic Acid process produce impure tail gas go deimpurity method, comprise the following steps:
A) described tail gas stream is sent into the first contactor containing ionic liquid, wherein, from tail gas stream, remove impurity;
B) described tail gas stream free from foreign meter for a part is imported the second contactor, wherein, tail gas stream free from foreign meter makes the ionic liquid regeneration be present in the second contactor; With
C) tail gas stream free from foreign meter of remainder is imported recovery unit.
This embodiment can be that one way is one-pass, or can be circulating, and make when a container is when adsorbing the impurity in feed gas stream, second container is regenerating.
Ionic liquid is the salts substances of ion completely, in very wide temperature range, is liquid usually within the scope of-96 DEG C to 200 DEG C.Ionic liquid is also nonvolatile, and the combination preferably by cation and anion comes special.
In one aspect of the invention, preferred ionic liquid is selected from lower group: based on imidazoline, pyridine, pyrrolin, guanidine, ammonium, phosphorus, the ionic liquid of sulfone (sulphonium), or 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 thiazolinyl.These groups can be selected from lower group: hydrogen, and contain straight or branched alkyl and the thiazolinyl of 1 to 12 carbon atom.Some amine groups, also can be combined in as thiocarbamide or amino in the cation in ionic liquid to improve chelating CO
2ability.In addition, hydroxyl also can be combined on cation.For an application-specific, need to consider cation and anion optimum organization to get up to realize the adsorption capacity of ionic liquid height and high heat endurance.
The present invention has following advantage relative to the tail gas treatment process in other Production of Terephthalic Acid process: efficiency is higher, and this is because ionic liquid is to carbon dioxide, carbon monoxide, the cause that the solubility of alkyl bromide and other harmful organic compounds is high; For the integrated process of the fixation in situ and conversion that remove these impurity; Separative element volume is little, so cost of investment is low; Needn't catalytic combustion unit, only regenerate a small amount of ionic liquid and non-renewable large adsorbent bed, so running cost is low.
detailed description of the present invention
Ionic liquid of the present invention is selected from lower group: imidazolinyl, pyridine radicals, pyrrolinyl, guanidine radicals, ammonium, phosphorus base, with the ionic liquid of sulfuryl, or 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
3and R
4various group be different alkyl and thiazolinyl.These groups can be selected from hydrogen, and contain straight or branched alkyl and the thiazolinyl of 1 to 12 carbon atom.Some amine groups, as on the cation that thiocarbamide or amino also can be combined in ionic liquid to improve chelating CO
2ability.In addition, hydroxyl also can be combined on cation.For a special application-specific, need to consider cation and anion optimum organization to get up to realize the adsorption capacity of ionic liquid height and high heat endurance.
Can ionic liquid be coated on the surface of base material, base material is added in the bed passing into tail gas to be clean.
Ionic liquid also can use by applying or encapsulate on porous bead and/or pill.Coated bead and/or pill can be loaded in container, can be the form of fixed bed, moving bed or fluid bed.
Also can by ionic liquid coating or the encapsulating bead of porous and/or pill, these beads and/or pill can be fixed to or be impregnated in the sheet material of stacked or lamination.The coated sheet including coated bead and/or pill is used by the mode be stacked, when stacking in a reservoir time, leave gap between each.Gas flow direction to be clean is parallel with sheet surface.When employing includes multichannel porous bead and/or pill in adsorbent bed, the resistance of gas flowing can be similar in all directions.In these cases gas flowing may with other bead individual and/or ball-shape at an angle, but the impact of adsorbent bed engineering design can be subject to.For in the application as packed bed, gas flowing or the axis along implantation, or in radial bed absorber situation radially.
If be coated in by ionic liquid material in monolithic substrate, gas is parallel to the passage in the block base material of monoblock type, to make pressure drop minimum by the flow direction of the block base material adsorbent of monoblock type.In some cases, made of one piece sorbent material has the passage be parallel to each other in one direction, and gas flow direction is only being parallel to the channel direction in sorbent material.
Ionic liquid can functionalised, and makes chemical group to be joined in ionic liquid structure to go, and gives the behaviour that ionic liquid is other.
The ionic liquid of a series of particular task can be utilized in the present invention.These ionic liquids can be modified the ability of carbon dioxide, bromomethane class and other the harmful organic compound improved in chelating Production of Terephthalic Acid process tail gas.By to the cation of ionic liquid and the modification of anion and/or combine the rate of adsorption and the adsorption capacity that improve these components.The display of amino acid 4-butyl-phosphonium class ionic liquid is to carbon dioxide high absorption capacity.
Go can realize removing the carbon monoxide in tail gas by catalyst is attached in ionic liquid.Giving ionic liquid has the group of catalytic activity that ionic liquid can be made to play the effect of catalyst, or as the solvent of catalyst..In order to make monoxide conversion, catalyst includes but not limited to and noble metal, as platinum, and the combination of palladium and rhodium.Oxidant for monoxide conversion can be the oxygen in feeding air, is dissolved in the oxidant in ionic liquid or custom-designed ionic liquid, as H
2o
2, NaClO etc.
When there being water in tail gas stream, a drying unit can be adopted before tail gas contacts with ionic liquid.This drying unit can be an adsorbent bed being filled with activated alumina.
By the component that ionic liquid is caught, 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.Such as, the technique combining fixing-conversion at ionic liquid situ can be adopted.
The bromomethane of chelating can remove at ionic liquid regeneration period, or by changing into hydrogen bromide removing.In order to transform alkyl bromide compound, catalyst includes but not limited to facilitation of hydrolysis or promotes the catalyst material of hydrogenation reaction as used herein.The product formed in alkyl bromide hydrolysis/hydrogenation process comprises hydrogen bromide and corresponding alcohols/hydro carbons.Hydrogen bromide can realize with being separated of alcohols/hydro carbons simultaneously.Can by the hydrogen bromide Returning oxidation reactor of recovery.
Ionic liquid of the present invention can be used for single bed system or has in the system of two or more.When adopting multibed system, this system can be circulating, and make a bed when adsorbing the impurity in feed gas stream, another bed is then regenerating.
Ionic liquid can be single ionic liquid, or the mixture of different kinds of ions liquid, can also combine as the solvent material of other functional compounds and they.
Ionic liquid may be used in the adsorbent bed of various system.Ionic liquid may be used for pressure-variable adsorption (PSA), Temp .-changing adsorption (TSA), become vacuum suction (vacuum swing adsorption) (VSA), Vacuum Pressure Swing Adsorption (vacuum pressure swing adsorption) is (in (VPSA) and Variable Composition absorption (CSA) process.
Typical PSA circulation comprises following sequential steps: pressurization, to discharge with product that (product withdrawal) adsorbs, exits, desorption, equalization of pressure and purging under lower pressure.
Although special embodiment describes the present invention, obviously, the present invention many other form and distortion be apparent for the professional person of those industry.Claims of the present invention should be considered to cover all such apparent forms and distortion, and they are within practicalness of the present invention and scope.
Claims (13)
1. one kind purifies the method for Production of Terephthalic Acid process tail gas, the method comprises sends tail gas stream into the container containing ionic liquid, wherein alkyl bromide compound, carbon dioxide and carbon monoxide are removed from this tail gas stream by being adsorbed in ionic liquid, wherein, described ionic liquid is selected from lower group: based on the ionic liquid of imidazoline, pyridine, pyrrolin, guanidine, ammonium, phosphorus, sulfone, or their mixture; Described ionic liquid has following structure:
In formula, R
1, R
2, R
3and R
4be hydrogen or different alkyl and thiazolinyl, this alkyl and thiazolinyl are selected from lower group: the straight or branched alkyl containing 1-12 carbon atom and thiazolinyl.
2. the method for claim 1, the method comprises the amine being selected from thiocarbamide and amino be present in described ionic liquid further.
3. the method for claim 1, the method comprises the hydroxyl be attached on described cation further.
4. the method for claim 1, is characterized in that, is coated on the surface of base material by described ionic liquid.
5. the method for claim 1, is characterized in that, is applied by described ionic liquid or is encapsulated on porous bead and pill.
6. from the impure tail gas of Production of Terephthalic Acid process, go a deimpurity method, wherein said impurity is selected from lower group: be alkyl bromide compound, carbon dioxide and carbon monoxide, the method comprises the following steps:
A) described tail gas stream is imported the first contactor containing ionic liquid, wherein, from tail gas stream, remove impurity;
B) described tail gas stream free from foreign meter for a part is sent into the second contactor containing ionic liquid, wherein, tail gas stream free from foreign meter is by the ionic liquid regeneration in the second contactor; With
C) tail gas stream free from foreign meter of remainder is imported recovery unit,
Wherein, described ionic liquid is selected from lower group: based on the ionic liquid of imidazoline, pyridine, pyrrolin, guanidine, ammonium, phosphorus, sulfone, or their mixture; Described ionic liquid has following structure:
In formula, R
1, R
2, R
3and R
4be hydrogen or different alkyl and thiazolinyl, this alkyl and thiazolinyl are selected from lower group: the straight or branched alkyl containing 1-12 carbon atom and thiazolinyl.
7. method as claimed in claim 6, it is characterized in that, the impure tail gas of described Production of Terephthalic Acid process is sent into described second contactor, described tail gas stream free from foreign meter for a part is sent into the first contactor containing ionic liquid, make described first contactor regeneration.
8. method as claimed in claim 6, the method comprises the amine being selected from thiocarbamide and amino be present in described ionic liquid further.
9. method as claimed in claim 6, the method comprises the hydroxyl be combined on described cation further.
10. method as claimed in claim 6, is characterized in that, be coated on the surface of base material by described ionic liquid.
11. methods as claimed in claim 6, is characterized in that, are applied by described ionic liquid or are encapsulated on porous bead and pill.
12. methods as claimed in claim 6, it is characterized in that, described method is selected from lower group: pressure-variable adsorption, Temp .-changing adsorption, becomes vacuum suction, Vacuum Pressure Swing Adsorption and Variable Composition adsorption method.
13. methods as claimed in claim 12, it is characterized in that, described method is cycling.
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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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|---|---|---|---|
| CN200910258681.0A CN102091498B (en) | 2009-12-14 | 2009-12-14 | Method for treating tail gas produced by terephthalic acid |
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| CN102091498A CN102091498A (en) | 2011-06-15 |
| CN102091498B true CN102091498B (en) | 2015-07-01 |
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| JP5888908B2 (en) * | 2011-09-09 | 2016-03-22 | 岩谷産業株式会社 | Concentration method of 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833752A (en) * | 2005-03-01 | 2006-09-20 | 林德股份公司 | Process for regeneration of adsorbents |
| CN101032677A (en) * | 2006-03-08 | 2007-09-12 | 波克股份有限公司 | Method of gas purification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833752A (en) * | 2005-03-01 | 2006-09-20 | 林德股份公司 | Process for regeneration of adsorbents |
| CN101032677A (en) * | 2006-03-08 | 2007-09-12 | 波克股份有限公司 | Method of gas purification |
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