CN105833667A - Renewable adsorbent for removing sulfur dioxide - Google Patents

Renewable adsorbent for removing sulfur dioxide Download PDF

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Publication number
CN105833667A
CN105833667A CN201610370757.9A CN201610370757A CN105833667A CN 105833667 A CN105833667 A CN 105833667A CN 201610370757 A CN201610370757 A CN 201610370757A CN 105833667 A CN105833667 A CN 105833667A
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China
Prior art keywords
scrubbing
absorbent
diamine
ethoxy
hydroxyethyl
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Pending
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CN201610370757.9A
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Chinese (zh)
Inventor
汪志和
崔广才
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Sichuan Yineng Kangsheng Environmental Protection Technology Co Ltd
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Sichuan Yineng Kangsheng Environmental Protection Technology Co Ltd
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Priority to CN201610370757.9A priority Critical patent/CN105833667A/en
Publication of CN105833667A publication Critical patent/CN105833667A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2056—Sulfur compounds, e.g. Sulfolane, thiols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention provides a renewable adsorbent for removing sulfur dioxide, comprising the following components according to parts by weight: 10-32 parts of a main component, 1-5 parts of an activator, 0.1-1 part of an antioxidant and 65-90 parts of water. The renewable absorbent provided herein uses a hydroxylethyldiamine sulfate as a body added with little activator and antioxidant and has the advantages such as high SO2 absorbing capacity, low energy consumption and high purity of renewed SO2, and the defects of the existing sulfur dioxide removal techniques are well solved.

Description

A kind of Regeneratable absorbent of scrubbing CO_2
Technical field
The present invention relates to environmental conservation and chemical gases separation field, particularly relate to a kind of de-from gaseous mixture Regeneratable absorbent except sulfur dioxide.
Background technology
The main flue gas desulfurization technique of domestic application at present, either external " the limestone Gypsum Fibrosum introduced Method ", " rotary spraying and drying method ", or domestic ammonia process, Dual alkali, sodium alkali, ammonia process etc., All have that by-product purposes is wide and garbage is difficult to dispose, absorbent can not regenerate, it is impossible to repeat profit With, while desulfurization, produce new CO2Or NH3The problems such as polluted by nitrogen, with China's sustainable development war Slightly do not correspond.
The patent No. 200710048743.6, inventor Xiao nine is high, Wang Zhi and etc., invention is a kind of from mixing Removing and reclaim the absorbent of sulfur dioxide in gas, its bulk composition is organic sun of 2-50% mass concentration The material that ion, the inorganic anion of 2-50% mass concentration form, the alkylol of 0.1-3% mass concentration Amine absorbs as the activator of scrubbing CO_2, the phenols of 0.1-0.2% mass concentration, quinones substance The antioxidant of agent, the metal-oxide of 0.1-0.2% mass concentration or inorganic salt are as the inhibition of absorbent Agent.It absorbs temperature 20-80 DEG C, regeneration temperature 85-130 DEG C, and by-product is the SO of 99% concentrations above2 Gas.
Number of patent application 201110192179.1, inventor hair pine and cypress, Wang Dong etc., a kind of Gao Xuan of invention Selecting property SO2Absorbent, its bulk composition be one or more unitary organic amines or binary organic amine, One or more weak acid or middle strong acid, antioxidant is the hindered phenol of 0.1-0.4%, and containing 0.1-0.2% Imidazoline corrosion inhibitor.It absorbs temperature 30-60 DEG C, regeneration temperature 105-130 DEG C, and by-product is 95% The SO of concentrations above2Gas.
Number of patent application 201410275142.9, inventor's Song Wan autumn, Ma Na etc., invention one removing The renewable serotonin absorbent of sulfur dioxide in flue gas, its bulk composition is N, N '-ethoxy second two Amine, diethylenetriamine, sulfolane, N methyldiethanol amine, monoethanolamine, hydroxyethylethylene diamine, piperazine One or more in piperazine, durol diamidogen or derivatives thereof, total content 8～10%；Auxiliary element 1 For 2-amino-2-methyl-1-propanol, 2-send pyridine ethanol, 1,8-menthanediamine, N, N-dihydroxy ethyl second Diamidogen, N-hydroxyethyl imidazole, tert-butylamine base ethanol, tertiary fourth aminoethoxyethanol, 1,2-(double tertiary fourths Aminoethoxy) one or more in ethane, total content 1～5%；Auxiliary element 2 is basic carbonate One or more in copper, vanadic anhydride, metavanadate, antimony potassium tartrate.It absorbs temperature 25-80 DEG C, regeneration temperature 90-130 DEG C, by-product is the SO of 98% concentrations above2Gas.
The Regeneratable absorbent that the present invention provides, based on hydroxyethyl diamine sulfate, adds a small amount of activation Agent and antioxidant, have SO2Absorbability is big, energy consumption is low, regeneration SO2Purity high, relatively Solve well the shortcoming that existing sulfur dioxide removal technology exists, it is achieved that flue gas desulfurization device efficient Change, resource, meet the developing goal of country's recycling economy.
Summary of the invention
Present invention aim to address subproblem present in existing sulfur dioxide removal technology, it is provided that one Plant the Regeneratable absorbent of scrubbing CO_2.
It is an object of the invention to be achieved through the following technical solutions:
A kind of Regeneratable absorbent of scrubbing CO_2, as follows including component and mass fraction:
Host component: 10-32 part；Activator: 1-5 part；Antioxidant: 0.1-1 part；Water 65-90 Part.
Further, described host component is hydroxyethyl diamine sulfate.
Further, described hydroxyethyl diamine is selected from N-hydroxyethyl piperazine, N, N '-bis-(ethoxy) Piperazine, N-hydroxyethyl imidazole, N, N '-bis-(ethoxy) imidazoles, N-hydroxyethyl-ethylenediamine, N, N '- Double (ethoxy) ethylenediamine, N-ethoxy propane diamine, N, N '-bis-(ethoxy) propane diamine, N- Ethoxy hexamethylene diamine, N, one or more in N '-bis-(ethoxy) propane diamine.
Further, in described hydroxyethyl diamine sulfate, the mol ratio of sulfate radical and hydroxyethyl diamine is 0.4-1.2。
Further, described sulfate radical is 0.6-1.0 with the mol ratio of hydroxyethyl diamine.
Further, described activator is secondary amine and alkyl alcoholamine.
Further, one or more in piperazine, imidazoles, 2-methylimidazole of described secondary amine.
Further, described alkyl alcoholamine includes diethanolamine, tert-butylamine base ethanol, 2-amino-2-first One or more of base-1-propanol.
Further, described antioxidant is hydroquinone, N, double (3-(3, the 5-di-t-butyl-4-of N- Hydroxy phenyl) propionyl) one or both in hexamethylene diamine.
Further, the pH value of described Regeneratable absorbent is 3-8.
Beneficial effects of the present invention: the absorbent that the present invention provides in use, uses low temperature absorption, adds Hot recycling, simultaneously by-product high concentration SO2, can be as producing liquid SO2, sulphuric acid, the product such as sulfur excellent Good raw material, makes SO2Turn waste into wealth, it is achieved that the high efficiency of flue gas desulfurization device, resource, meet state The developing goal of family's recycling economy.
This absorbent absorbs the SO in gaseous mixture at low temperature 20-60 DEG C2Gas, high temperature 85-120 DEG C Lower parsed, produced the concentration SO more than 99% (butt)2Side-product, absorbent obtains again Raw, recycle.
Accompanying drawing explanation
Fig. 1 be employed in embodiment containing SO2Process of desulfurizing gases flow chart.
Detailed description of the invention
In order to the present invention is better described, below in conjunction with the accompanying drawing in the embodiment of the present invention, real to the present invention The technical scheme executed in example is clearly and completely described.
Embodiment 1
Certain chemical company uses H2S burns acid-making process, for industry restructuring, extracts 10000Nm out3/h Combustion gas reclaims SO2, produce liquid SO2.SO in gas2Content is 242845mg/Nm3(8.5%), Temperature is 200 DEG C, pressure: 10kPa, uses such as the technological process of accompanying drawing 1:
Antacid flue gas initially enters water scrubber 1 dedusting cooling, is re-fed into absorption tower 2, the SO in flue gas2 Being absorbed by absorbent, exit gas is vented.Absorb SO2After rich solution entered lean by the bottom of tower through rich solution pump 3 Rich solution heat exchanger 4, enters regenerator 5 top after reclaiming heat.The SO desorbed2Together with steam through cold After condenser 9 cooling, it is separated off moisture through gas-liquid separator 10, obtains the product SO of purity 99.5%2 Gas, Song Xia workshop section uses.The condensed water separated that is condensed in regeneration gas is delivered to by reflux pump 11 again Raw tower 5 top.Rich solution enters from regenerator top, by stripping desorption part SO2, subsequently into again Boiling device 6 so that it is in SO2Desorbing further.Desorbing SO2After lean solution by regenerator 5 end flow out, warp After lean pump 7, poor rich liquid heat exchanger 4, enter top, absorption tower 2 through lean solution cooler 8.Absorbent Cyclic constitutes continuous absorption and desorbing SO2Technical process.
Absorbent consists of: N-hydroxyethyl piperazine sulfate 28% (weight), diethanolamine+piperazine 5% (weight), hydroquinone 0.1% (weight), remaining composition are water.Absorbent pH value 3～6.8.
Relevant parameter is as shown in the table:
Utilizing this absorbent formula, desulfuration efficiency is high, product SO2Gas content is high, steady quality.
Embodiment 2
Certain oil plant CLAUS sulfur recovery unit, SO in reformed gas2Content is 0.9%, and temperature is 200 DEG C, Pressure: 4kPa, uses such as the technological process of accompanying drawing 1:
Convert gas and initially enter water scrubber 1 dedusting cooling, be re-fed into absorption tower 2, the SO in flue gas2Quilt Absorbent absorbs, and exit gas is vented.Absorb SO2After rich solution entered rich or poor by the bottom of tower through rich solution pump 3 Liquid heat exchanger 4, enters regenerator 5 top after reclaiming heat.The SO desorbed2Condensed together with steam After device 9 cooling, it is separated off moisture through gas-liquid separator 10, obtains the product SO of purity 99.5%2Gas, Song Xia workshop section uses.The condensed water separated that is condensed in regeneration gas is delivered to regenerator by reflux pump 11 5 tops.Rich solution enters from regenerator top, by stripping desorption part SO2, subsequently into reboiler 6, Make SO therein2Desorbing further.Desorbing SO2After lean solution by regenerator 5 end flow out, through lean pump 7, After poor rich liquid heat exchanger 4, enter top, absorption tower 2 through lean solution cooler 8.Absorbent cyclic structure Become continuous absorption and desorbing SO2Technical process.
Solution composition is: N, N '-bis-(ethoxy) piperazine sulfate+N-hydroxyethyl piperazine sulfate 25% (weight), piperazine 5% (weight), hydroquinone 0.16% (weight), remaining composition are water, Absorbent pH value 3～6.8.
Relevant parameter is as shown in the table:
Utilizing this solution formula, absorbent detergent power is strong, can be by the SO in flue gas2It is removed to 35 mg/Nm3Below, it is achieved ultra-clean discharge.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not Being confined to this, any those familiar with the art, can in the technical scope of present disclosure The change readily occurred in or replacement, all should contain within protection scope of the present invention.Therefore, this Bright protection domain should be as the criterion with the protection domain of claims.

Claims (10)

1. the Regeneratable absorbent of a scrubbing CO_2, it is characterised in that include component and quality Number is as follows:
Host component: 10-32 part；Activator: 1-5 part；Antioxidant: 0.1-1 part；Water 65-90 Part.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 1, it is characterised in that Described host component is hydroxyethyl diamine sulfate.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 2, it is characterised in that Described hydroxyethyl diamine is selected from N-hydroxyethyl piperazine, N, N '-bis-(ethoxy) piperazine, N-ethoxy Imidazoles, N, N '-bis-(ethoxy) imidazoles, N-hydroxyethyl-ethylenediamine, N, N '-bis-(ethoxys) Ethylenediamine, N-ethoxy propane diamine, N, N '-bis-(ethoxy) propane diamine, N-ethoxy hexamethylene diamine, N, N ' one or more in-bis-(ethoxy) propane diamine.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 2, it is characterised in that In described hydroxyethyl diamine sulfate, sulfate radical is 0.4-1.2 with the mol ratio of hydroxyethyl diamine.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 4, it is characterised in that Described sulfate radical is 0.6-1.0 with the mol ratio of hydroxyethyl diamine.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 1, it is characterised in that Described activator is secondary amine and alkyl alcoholamine.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 6, it is characterised in that One or more in piperazine, imidazoles, 2-methylimidazole of described secondary amine.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 6, it is characterised in that Described alkyl alcoholamine includes diethanolamine, tert-butylamine base ethanol, the one of 2-amino-2-methyl-1-propanol Or it is multiple.
The Regeneratable absorbent of scrubbing CO_2 the most according to claim 1, it is characterised in that Described antioxidant is hydroquinone, N, and N-is double (3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) One or both in hexamethylene diamine.
10. according to the Regeneratable absorbent of the arbitrary described scrubbing CO_2 of claim 1-9, its feature Being, the pH value of described Regeneratable absorbent is 3-8.
CN201610370757.9A 2016-05-27 2016-05-27 Renewable adsorbent for removing sulfur dioxide Pending CN105833667A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108479311A (en) * 2018-04-17 2018-09-04 安徽华铂再生资源科技有限公司 A kind of method of cyclic absorption secondary lead smelting and ring collection sulfur dioxide in flue gas
CN110624364A (en) * 2019-09-12 2019-12-31 中国石油化工股份有限公司 Organic absorbent for removing sulfur dioxide in mixed gas and preparation method
CN110876878A (en) * 2018-09-06 2020-03-13 中国石油化工股份有限公司 SO2Absorbent and absorption of SO2Method (2)
CN112138518A (en) * 2019-06-26 2020-12-29 中石化南京化工研究院有限公司 High-selectivity flue gas desulfurization absorbent and preparation method thereof
CN112915729A (en) * 2021-02-03 2021-06-08 四川大学 High-efficiency SO absorption device2Renewable morpholine composite absorbent
CN116603369A (en) * 2023-04-28 2023-08-18 成都益志科技有限责任公司 Absorbent capable of efficiently absorbing sulfur dioxide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1557294A (en) * 1975-11-10 1979-12-05 Davy Powergas Inc Sulphur dioxide removal and recovery
EP0696469A1 (en) * 1994-08-09 1996-02-14 Elf Atochem North America, Inc. Removal of sulphur dioxide from gaseous streams
CN101274204A (en) * 2007-03-28 2008-10-01 成都华西化工研究所 Absorbing agent for removing and recovering sulfur dioxide from gaseous mixture
CN101721884A (en) * 2009-12-10 2010-06-09 攀枝花新钢钒股份有限公司 Smoke desulphurization agent and smoke desulphurization method
CN104774665A (en) * 2015-01-29 2015-07-15 中国石油天然气集团公司 Activating MDEA solution for deep deacidification of liquefied natural gas
CN105080326A (en) * 2015-09-16 2015-11-25 广东电网有限责任公司电力科学研究院 Mixed absorption liquid for capturing carbon dioxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1557294A (en) * 1975-11-10 1979-12-05 Davy Powergas Inc Sulphur dioxide removal and recovery
EP0696469A1 (en) * 1994-08-09 1996-02-14 Elf Atochem North America, Inc. Removal of sulphur dioxide from gaseous streams
CN101274204A (en) * 2007-03-28 2008-10-01 成都华西化工研究所 Absorbing agent for removing and recovering sulfur dioxide from gaseous mixture
CN101721884A (en) * 2009-12-10 2010-06-09 攀枝花新钢钒股份有限公司 Smoke desulphurization agent and smoke desulphurization method
CN104774665A (en) * 2015-01-29 2015-07-15 中国石油天然气集团公司 Activating MDEA solution for deep deacidification of liquefied natural gas
CN105080326A (en) * 2015-09-16 2015-11-25 广东电网有限责任公司电力科学研究院 Mixed absorption liquid for capturing carbon dioxide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108479311A (en) * 2018-04-17 2018-09-04 安徽华铂再生资源科技有限公司 A kind of method of cyclic absorption secondary lead smelting and ring collection sulfur dioxide in flue gas
CN110876878A (en) * 2018-09-06 2020-03-13 中国石油化工股份有限公司 SO2Absorbent and absorption of SO2Method (2)
CN112138518A (en) * 2019-06-26 2020-12-29 中石化南京化工研究院有限公司 High-selectivity flue gas desulfurization absorbent and preparation method thereof
CN110624364A (en) * 2019-09-12 2019-12-31 中国石油化工股份有限公司 Organic absorbent for removing sulfur dioxide in mixed gas and preparation method
CN112915729A (en) * 2021-02-03 2021-06-08 四川大学 High-efficiency SO absorption device2Renewable morpholine composite absorbent
CN116603369A (en) * 2023-04-28 2023-08-18 成都益志科技有限责任公司 Absorbent capable of efficiently absorbing sulfur dioxide

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Application publication date: 20160810