CN102218260B - Absorbent used for removing sulfides in malodorous gases - Google Patents

Absorbent used for removing sulfides in malodorous gases Download PDF

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CN102218260B
CN102218260B CN 201010144818 CN201010144818A CN102218260B CN 102218260 B CN102218260 B CN 102218260B CN 201010144818 CN201010144818 CN 201010144818 CN 201010144818 A CN201010144818 A CN 201010144818A CN 102218260 B CN102218260 B CN 102218260B
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weight
absorbent
component
sodium
tannin
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CN102218260A (en
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何庆生
张建成
刘献玲
曹玉红
田小峰
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China Petrochemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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Abstract

The invention provides an absorbent used for removing sulfides in malodorous gases and a preparation method thereof, and aims at solving the problems that the existing desulfurization methods have high operating cost, poor desulfurization effects and high solvent cost. The absorbent is prepared from the following raw materials of water, sodium hydroxide or potassium hydroxide, a sodium salt of ethylene diamine tetra-acetic acid (EDTA) or sodium tartrate, p-benzoquinone or tannin, vanadium pentoxide or sodium metavanadate and ethanolamine according to the preparation method provided by the invention. The absorbent can absorb hydrogen sulfide, mercaptans, thioethers and other sulfur-containing acidic gases, and has low cost and a wide application range, the removal rate of hydrogen sulfide is more than 99% and the removal rate of other organic sulfurs is more than 90%.

Description

A kind of absorbent that removes sulfides in malodorous gases
Technical field
The invention belongs to the master gas technical field, relate to specifically a kind of absorbent that removes sulfides in malodorous gases.
Background technology
Petroleum refining industry is the key industry that produces odor pollution, and the chemical reaction of complexity can produce a large amount of H in the petroleum refining process 2The odorants such as S, COS, mercaptan, thioether.These materials enter atmosphere in modes such as discharging, volatilization, leakages in production, transporting procedures, cause the pollution sources different odor pollution of degree on every side.In recent years, increasing enterprise begins the processing foreign sour crude.It is more outstanding that especially odor pollution problem of environmental pollution becomes.The surrounding environment of each oil plant all faces the trend that odor pollution increases the weight of day by day.
The method that removes these Stenchy sulfides is a lot, is divided into two kinds of dry desulfurization and wet desulphurizations.The method of wet desulphurization both at home and abroad mainly contains at present: anthraquinone disulphonate method (ADA), tannin extract method (TV method), phthalocyanine cobalt sulfonate method, Complexing Iron, amine method desulfurization etc.
Patent documentation CN1421264 discloses a kind of absorption liquid that removes sulfide from admixture of gas, and this absorption liquid comprises (1) main absorbent, is comprised of sterically hindered amines (I) and N methyldiethanol amine (II); (2) cosolvent (III).Adopt this absorption liquid, can be simultaneously with H 2S, COS, mercaptan, thioether sulfides remove.This absorption liquid is take organic amine as main body, and operating cost is expensive, and organic solvent amine itself is degraded easily, need to remove heat stable salt.
Patent documentation CN1384046 discloses a kind of desulfurizing tanning extract process, and this technique is squeezed into the solution circulation groove with alkaline tannin extract solution, and the self-loopa groove out enters splitting of system after the pressurization after filtration and takes off tower, the H in the absorption of gases 2S takes off tower solution out and enters to split and take off regenerator by splitting, the good solution of regeneration by tower bottom flow to the solution circulation groove, after filtration pressurized circulation use; Desulfuration solution is out delivered to become by filter-press from circulating slot and is taken off tower, the H in the absorption of gases 2S takes off tower solution out by change and enters change precipitation liquid regenerator, and the solution that regeneration is good takes off regenerator out by change, enters to become precipitation liquid circulating slot, and after filtration pressurization so recycles again.The method forms complexity for the foul gas of some cell arrangement discharging of petrochemical enterprise, contains the Various Complex organic matter, and hydrogen sulfide, organic sulfur content are all higher.Utilize existing desulfurizing agent and method, be difficult to effective desulfurization.
Patent documentation CN1887406 discloses a kind of H that removes from gaseous mixture 2The solvent of S, this solvent are that the organic amine that adds a kind of secondary amine and have space steric effect in take water or sulfolane as the N methyldiethanol amine solution of main body is as activator, in order to from containing or do not contain CO 2Mist in remove the method for hydrogen sulfide.The invention provides two groups of solution formulas: (1) is suitable for never containing in organic sulfur or the low organic sulfur compound gas and removes H 2The solution formula of S is: N methyldiethanol amine 30～50 % by weight, secondary amine 1～10 % by weight, sterically hindered amines 1～15 % by weight, and all the other components are water; (2) be suitable for from contain volatile sulfur gases, removing H 2The solution formula of S and part organic sulfur is: N methyldiethanol amine 30～40 % by weight, secondary amine 1～5 % by weight, sterically hindered amines 1～15 % by weight, water 5 % by weight, all the other components are sulfolane.This solvent is organic amine solvent, hydrogen sulfide and organic sulfur are all had preferably removal effect, but solvent cost is very high.
Summary of the invention
In order to solve the operating cost height that exists in the above-mentioned sulfur method, bad desulfurization effects, problem that solvent cost is high, the invention provides a kind of absorbent that can remove sulfides in malodorous gases.The sulfuric acid gases such as this absorbent energy absorbing hydrogen sulphide, mercaptan, thioether do not produce secondary pollution after the absorption, waste liquid is easily processed, and does not contain elemental sulfur in the product, has avoided reactor plugs.
The raw material of the absorbent that removes sulfides in malodorous gases provided by the invention form and content as follows:
(A) diluent 67～85 % by weight,
(B) strong inorganic base 10～30 % by weight,
(C) complex compound cosolvent 0.5～2 % by weight,
(D) catalyst 0.1～1 % by weight,
(E) oxidant 0.5～2 % by weight,
(F) strengthen absorbent 1～4 % by weight.
Above-mentioned raw materials mixed, reacts by following preparation method can make absorbent of the present invention:
(1) ratio according to each component in the raw material calculates the required weight of each component;
(2) add in the container first and should add 60%～80% of component (A) total amount, the component (C) that adds afterwards capacity, and be stirred to fully dissolving, then the component (B) that adds capacity, and be stirred to dissolving, dissolve, react in the adding container with the component (D) of capacity with (E) at last;
(3) all components adds component (F) after all dissolving and temperature are down to below 40 ℃ in container in container, replenishes simultaneously to add remaining component (A) and mix, and so far absorbent preparation is finished.
Wherein, described diluent (A) is pure water or running water, is used for diluting the active ingredient in the absorbent;
Described strong inorganic base (B) is NaOH or potassium hydroxide, preferred NaOH, and this component is main chemical absorbing component, and sulfide is sour gas, and most component all can react with highly basic;
Described complex compound cosolvent (C) is sodium salt (EDTA) or the sodium potassium tartrate tetrahydrate of ethylenediamine tetra-acetic acid, or both mixtures, Main Function is complexing part metals ion, prevents that a small amount of ion from producing precipitation, shields some active metallic ion and participates in reaction;
Described catalyst (D) is 1,4-benzoquinone or tannin, plays catalytic action, itself can be oxidized by oxygen to be oxidizing substance, has the function of catching oxygen in the foul gas;
Described oxidant (E) is vanadic anhydride or sodium metavanadate, plays oxidation, and itself can be by the reduction of the sulfide in the foul gas, and the Low Valent Vanadium of producing simultaneously can be oxidized to the high price vanadium by oxygen and catalyst (D);
Described reinforcement absorbent (F) is monoethanolamine, and the process of absorbing hydrogen sulphide is the Physical Absorption process.
According to double-film theory, absorb resistance in the Physical Absorption process and comprise air film resistance and liquid-film resistance, the gas phase total absorption coefficient is:
1 K G = 1 k G + 1 Hk L
In MODEL OF CHEMICAL ABSORPTION PROCESS, chemical reaction velocity has great impact to absorption process, divides according to chemical reaction velocity, and may there be three kinds of reactions in MODEL OF CHEMICAL ABSORPTION PROCESS: transient response, fast reaction and long response time.
Component among the present invention (B) absorbing hydrogen sulphide is irreversible chemical reaction at a slow speed, when component (B) when concentration ratio is higher, can be considered at a slow speed irreversible chemical reaction.The MODEL OF CHEMICAL ABSORPTION PROCESS resistance can be similar to Physical Absorption.But component (F) absorbing hydrogen sulphide is instantaneous reversible reaction, can greatly strengthen absorption process with component (F) solution absorption hydrogen sulfide.Component (F) boiling point substance is high, good stability, is difficult for decomposing.The reaction of component (F) absorbing hydrogen sulphide generates salt, and is with component (B) reaction, again born again.Like this, in component (B), add component (F), can in absorption process, play the effect of similar catalyst.
The principle that this absorbent absorbs oxidation of sulfureted hydrogen, mercaptan, thioether is as follows:
H 2S+2OH -→S 2-+2H 2O S 2-+4[O]+OH→SO 4 2-+H 2O
RSH+OH -→RS -+H 2O RSH+[O]+OH -→(RS) 2+H 2O
(RS) 2+[O]+OH -→SO 4 2-+H 2O+RCOO -
Absorbent of the present invention is a kind of volatility gases containing stench sulphureous gases special absorptive agent of function admirable, can be applicable to refine oil, the foul waste gas of the factories such as chemical industry, natural gas administers.The sulfuric acid gases such as this absorbent can absorbing hydrogen sulphide, mercaptan, thioether, do not produce secondary pollution after the absorption, namely do not produce DMDS, the product that generates is high price sulfate radical, inferior sulfate radical, thiosulfate anion etc., waste liquid is easily processed, do not contain elemental sulfur in the product, avoided reactor plugs.This absorbent cost is low, nontoxic, the scope of application is wide, remove in the waste gas hydrogen sulfide content from several milligrams/cubic metres to thousands of milligram/cubic meters, other organic sulfur contents can both reach satisfied effect from several milligrams/cubic metres to hundreds of milligrams/cubic metres, the hydrogen sulfide stripping rate is more than 99%, and other organic sulfur removal rates are more than 90%.
The specific embodiment:
The present invention will be further described below in conjunction with specific embodiment, and embodiment 1～6 is the preparation example of absorbent of the present invention, and embodiment 7 is the effect example of absorbent of the present invention.
Embodiment 1
Raw material composition and content are as follows:
(A) running water of 76.5 % by weight;
(B) NaOH of 20 % by weight;
(C) sodium potassium tartrate tetrahydrate of 1 % by weight;
(D) 1,4-benzoquinone of 0.5 % by weight;
(E) sodium metavanadate of 1 % by weight;
(F) monoethanolamine of 1 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.
Embodiment 2
Raw material composition and content are as follows:
(A) running water of 76 % by weight;
(B) NaOH of 20 % by weight;
(C) sodium potassium tartrate tetrahydrate of 1 % by weight;
(D) 1,4-benzoquinone of 1 % by weight;
(E) sodium metavanadate of 1 % by weight;
(F) monoethanolamine of 1 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.
Embodiment 3
Raw material composition and content are as follows:
(A) running water of 76.5 % by weight;
(B) NaOH of 20 % by weight;
(C) EDTA of 1 % by weight;
(D) 1,4-benzoquinone of 1 % by weight;
(E) sodium metavanadate of 0.5 % by weight;
(F) monoethanolamine of 1 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.
Embodiment 4
Raw material composition and content are as follows:
(A) running water of 76 % by weight;
(B) NaOH of 20 % by weight;
(C) EDTA of 1 % by weight;
(D) tannin of 1 % by weight;
(E) vanadic anhydride of 1 % by weight;
(F) monoethanolamine of 1 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.
Embodiment 5
Raw material composition and content are as follows:
(A) running water of 76.5 % by weight;
(B) NaOH of 20 % by weight;
(C) EDTA of 1 % by weight;
(D) tannin of 1 % by weight;
(E) vanadic anhydride of 0.5 % by weight;
(F) monoethanolamine of 1 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.
Embodiment 6
Raw material composition and content are as follows:
(A) running water of 73 % by weight;
(B) NaOH of 20 % by weight;
(C) EDTA of 1 % by weight;
(D) tannin of 1 % by weight;
(E) vanadic anhydride of 1 % by weight;
(F) monoethanolamine of 4 % by weight.
Above-mentioned raw materials is prepared by preparation method of the present invention can makes absorbent of the present invention.The absorbent color of each embodiment and character pair ratio see Table 1.
The color of table 1 embodiment and proterties
Project Color Proterties
Embodiment 1 Rufous A small amount of white solid
Embodiment 2 Rufous A small amount of white solid
Embodiment 3 Rufous Solution is more transparent
Embodiment 4 Bronzing A small amount of brown solid
Embodiment 5 Bronzing A small amount of brown solid
Embodiment 6 Bronzing A small amount of brown solid
The solids of sedimentation that solid particle among embodiment 1 and the embodiment 2 does not have complete complexing dissolving to generate for metal ions such as a small amount of calcium, magnesium.Mixture after embodiment 4, embodiment 5 and embodiment 6 produce is the bronzing transparency liquid, and a small amount of sediment is arranged at the solution bottom, and the inert impurities in this sediment catalyst is not produced novel substance with other substance reactions, does not affect desulfurized effect.
Embodiment 7
Take the common fillers tower as absorption equipment, absorbent of the present invention is carried out the test of hydrogen sulfide absorption Contrast on effect, the concentration of hydrogen sulfide of foul gas is 1500～5000mg/m 3, test result sees Table 2.
The absorbent of each embodiment of table 2 removes the effect of hydrogen sulfide
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Air inlet H 2S content, mg/m 3 3260 2160 3650 3780 3490 3150
H gives vent to anger 2S content, mg/m 3 10.8 9.5 11.2 5.9 7.1 2.6
H 2The S removal efficiency, % 99.7 99.6 99.7 99.8 99.8 99.9
Can find out by the tables of data 2 behind the analytical test: embodiment 4, embodiment 5 and embodiment 6 assimilation effects obviously are better than embodiment 1, embodiment 2 and embodiment 3; Comparative example 4 and embodiment 6 can find out that the content of strengthening absorbent is high, good absorbing effect.
Form also discovery by the material after the further analysis absorption: the absorption product Central Asia sulfate concentration of embodiment 4 and embodiment 6 is starkly lower than other embodiment, by analyzing possible reason be: 1,4-benzoquinone generates a small amount of hydroquinones in the process that participates in reaction, and hydroquinones has stabilization to sulphite; The a little higher than sodium metavanadate of the oxidation effectiveness of vanadic anhydride.
The desulfurization oxidation effectiveness of Comprehensive Comparison embodiment 6 is better, and embodiment 6 has been carried out the test of mercaptan assimilation effect, and test result sees Table 3.
The absorbent of table 3 embodiment 6 removes the effect of mercaptan
The air inlet mercaptans content, mg/m 3 207.5 134.4 121.9
The mercaptans content of giving vent to anger, mg/m 3 0 0 0
The mercaptan removal efficiency, % 100 100 100

Claims (2)

1. an absorbent that removes sulfides in malodorous gases is characterized in that, raw material composition and the content of this absorbent are as follows:
(A) diluent 67～85 % by weight,
(B) strong inorganic base 10～30 % by weight,
(C) complex compound cosolvent 0.5～2 % by weight,
(D) catalyst 0.1～1 % by weight,
(E) oxidant 0.5～2 % by weight,
(F) strengthen absorbent 1～4 % by weight;
This absorbent prepares by following preparation method:
(1) ratio according to each component in the raw sorbent calculates the required weight of each component;
(2) add in the container first and should add 60%～80% of component (A) total amount, the component (C) that adds afterwards capacity, and be stirred to fully dissolving, then the component (B) that adds capacity, and be stirred to dissolving, dissolve, react in the adding container with the component (D) of capacity with (E) at last;
(3) all components adds component (F) after all dissolving and temperature are down to below 40 ℃ in container in step (2), replenishes simultaneously to add remaining component (A) and mix;
Wherein, described diluent (A) is pure water or running water; Described strong inorganic base (B) is NaOH or potassium hydroxide; Described complex compound cosolvent (C) is sodium salt or the sodium potassium tartrate tetrahydrate of ethylenediamine tetra-acetic acid, or both mixtures; Described catalyst (D) is 1,4-benzoquinone or tannin; Described oxidant (E) is vanadic anhydride or sodium metavanadate; Described reinforcement absorbent (F) is monoethanolamine.
2. absorbent according to claim 1 is characterized in that described diluent is running water, and strong inorganic base is NaOH, and the complex compound cosolvent is the sodium salt of ethylenediamine tetra-acetic acid, and catalyst is tannin, and oxidant is sodium metavanadate.
CN 201010144818 2010-04-13 2010-04-13 Absorbent used for removing sulfides in malodorous gases Active CN102218260B (en)

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CN103285714B (en) * 2013-06-17 2015-07-22 连云港盛和生物科技有限公司 Method for removing odor organic gas
CN103432883B (en) * 2013-07-09 2016-02-03 南京信息工程大学 A kind of flue gas laminated desulfurizer
CN106823693B (en) * 2017-03-28 2019-08-27 中北大学 A kind of deep desulfuration absorbent for smoke-gas wet desulfurization
CN115893711B (en) * 2022-10-26 2023-10-31 中国石油化工股份有限公司 Treatment method suitable for organic sulfur in fracturing flowback fluid of oil and gas field

Citations (7)

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Publication number Priority date Publication date Assignee Title
US4808765A (en) * 1987-07-17 1989-02-28 The Dow Chemical Company Sulfur removal from hydrocarbons
US5589149A (en) * 1993-11-09 1996-12-31 Union Carbide Chemicals & Plastics Technology Corporation Process for absorption of mercaptans
CN1421264A (en) * 2002-12-11 2003-06-04 南化集团研究院 Absorbing liquid for eliminating sulfide from gas mixture
EP1196233B1 (en) * 1999-07-15 2004-10-13 Basf Aktiengesellschaft Method for removing mercaptans from fluid fluxes
CN1621133A (en) * 2003-11-24 2005-06-01 杨军 Absorption liquid for gas desulfurization and its application
CN1887406A (en) * 2005-06-27 2007-01-03 成都华西化工研究所 Solvent for eliminating H2S from gas mixture
CN101249379A (en) * 2008-04-04 2008-08-27 中国石油化工集团公司 Malodorous gas processing assembly technique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808765A (en) * 1987-07-17 1989-02-28 The Dow Chemical Company Sulfur removal from hydrocarbons
US5589149A (en) * 1993-11-09 1996-12-31 Union Carbide Chemicals & Plastics Technology Corporation Process for absorption of mercaptans
EP1196233B1 (en) * 1999-07-15 2004-10-13 Basf Aktiengesellschaft Method for removing mercaptans from fluid fluxes
CN1421264A (en) * 2002-12-11 2003-06-04 南化集团研究院 Absorbing liquid for eliminating sulfide from gas mixture
CN1621133A (en) * 2003-11-24 2005-06-01 杨军 Absorption liquid for gas desulfurization and its application
CN1887406A (en) * 2005-06-27 2007-01-03 成都华西化工研究所 Solvent for eliminating H2S from gas mixture
CN101249379A (en) * 2008-04-04 2008-08-27 中国石油化工集团公司 Malodorous gas processing assembly technique

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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No.

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