CN109772134A - A kind of circularly removing H2S and SO2And the method for recycling sulphur - Google Patents

A kind of circularly removing H2S and SO2And the method for recycling sulphur Download PDF

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Publication number
CN109772134A
CN109772134A CN201910021462.4A CN201910021462A CN109772134A CN 109772134 A CN109772134 A CN 109772134A CN 201910021462 A CN201910021462 A CN 201910021462A CN 109772134 A CN109772134 A CN 109772134A
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organic base
solvent
tower
passed
absorb
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CN109772134B (en
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赵文波
谢旭豪
贾庆明
徐志勇
陈媛
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The present invention discloses a kind of circularly removing H2S and SO2And the method for recycling sulphur, belong to energy-saving and emission-reduction and field of gas purification.The method of the invention is by H2S or SO2SO is absorbed with into tower2Or H2The organic Alkali absorption that can be also not utilized in the organic base of reaction regeneration and process while organic base-solvent reaction of S, regenerated organic base and unused organic base absorb H2S or SO2Next reactive absorption tower can be directly entered after being separated by solid-liquid separation by knockout tower to utilize.The invention enables traditional High Temperature Gas phase claus process to realize under conditions of liquid phase is mild, not only breaches high temperature to the thermal balance limitation of claus reaction to improve conversion ratio;And it solves industrially utilize organic amine removal H simultaneously2S and SO2Serious problem is lost in existing desorption energy consumption high-selenium corn agent;It is carried out in one single secondly, this method will be absorbed with reacting, is more in line with the idea of Green Chemistry.

Description

A kind of circularly removing H2S and SO2And the method for recycling sulphur
Technical field
The present invention relates to a kind of circularly removing H2S and SO2And the method for recycling sulphur, belong to energy-saving and emission-reduction and gas purification neck Domain.
Background technique
H2S is a kind of poisonous and harmful sour gas for having intense irritation smell, is largely present in oil plant and natural gas In factory's sulfur removal technology, and SO2It is also a kind of irritant mordant sour gas of smell, is largely present in coal-burning utilities In.H2S and SO2Also it can exist simultaneously in coal bed gas, they can cause atmospheric environment seriously to pollute, it is therefore necessary to it Trapping purification, which reaches national emission standard, to discharge.H at present2S and SO2After the main concentration trapping by organic amine absorbent again Next technique is sent into through medium temperature desorption to be utilized.There are the higher problems of the serious energy consumption of absorbent volatilization loss for the process, and For H2S using being to carry out claus reaction to be converted into sulphur simple substance, traditional gas phase claus reaction needs first will be a part of The H of trapping is concentrated2S high-temperature oxydation is at SO2Then the reaction is carried out in the condition of catalyst and high fever again, the condition of high fever is not The problem that only energy consumption can be brought excessively high but also can inhibit claus process return middle exothermic reaction, causes conversion ratio low, from And last tail gas also needs fine desulfurizing technology, entire complex technical process is cumbersome, and process is longer.
Summary of the invention
The purpose of the present invention is to provide a kind of circularly removing H2S and SO2And the method for recycling sulphur, this method are effectively improved Existing H2S and SO2The gentle phase Crouse of removing sulfuldioxide recycles the deficiency of sulphur technology, while planning as a whole to dispose to the greatest extent rationally Using exhaust gas resource, specifically includes the following steps:
(1) contain H2The industrial waste gas of S is from H2S absorbing reaction tower bottom is passed through, organic base-solvent and from subsequent technique be circulated throughout come Absorb SO2Organic base-solvent from H2S absorbing reaction tower top flows into, and absorbs SO2Organic base-solvent and H2S occurs Liquid-phase claus reaction generates sulphur simple substance and regenerates organic base absorbent, and unused organic base-solvent and liquid phase Crouse The organic base of reaction regeneration can also absorb the H being passed through2S, exhaust gas after processing is arranged from tower top, from H2S absorbing reaction tower bottom row Reaction solution out is passed through in knockout drum, produces sulphur simple substance from knockout drum bottom, will absorb H from knockout drum top2S's is organic Alkali-solvent is passed through SO2Absorbing reaction tower;
(2) contain SO2Industrial waste gas be passed through SO from bottom2Absorbing reaction tower, in SO2H is absorbed in absorbing reaction tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower realizes that circular response absorbed Journey;Circular response soak time is any time in step (1) and (2).
Preferably, H in step (1) of the present invention2S partial pressure is 0.1%~10% atm.
Preferably, the organic base in organic base-solvent of the present invention are as follows: tetramethylguanidine, 3- pyridinemethanol, cyclohexylamine, N-methylcyclohexylamine, N, N- dimethyl cyclohexyl amine, n,N-Dimethylaniline, 1,8- diazabicylo, 11 carbon -7- alkene (DBU), One of dimethylethanolamine, diisopropanolamine (DIPA), solvent are sulfolane, diethylene glycol monomethyl ether, ethyl alcohol, water, N- methyl pyrrole One of pyrrolidone.
Preferably, the molar content of the organic base in organic base-solvent of the present invention is 30%~75%.
Preferably, step (2) SO of the present invention2Partial pressure is 1%~15% atm.
The principle of the invention are as follows:
Firstly, sour gas H2S or SO2After being passed through the liquid-phase system containing organic base, organic base can be with acid SO2Or H2During S occurs SO is absorbed with reaction2Or H2S;Principle of absorption by taking n,N-Dimethylaniline as an example: n,N-Dimethylaniline and SO2Or H2S hair Raw neutralization reaction, is respectively formed: electon transfer product n,N-Dimethylaniline SO2And proton translocation product N, N- diformazan Base aniline-sulfur hydrogen salt, specific reaction equation are as follows:
N,N-Dimethylaniline and SO2Neutralization reaction generates electon transfer product principle:
N,N-Dimethylaniline and H2S neutralization reaction generates proton translocation product principle:
Then, it is based on SO2And H2The comproportionation reaction of S:, SO2Or H2S is by organic Alkali absorption After forming corresponding product, absorption product can be with the H that is passed through2S or SO2Comproportionation reaction occurs for gas, generates elemental sulfur and water is same When absorbent regeneration organic base;SO is absorbed by taking n,N-Dimethylaniline as an example2Or H2The product and H that S is formed2S or SO2Reaction Equation is as follows:
N,N-Dimethylaniline absorbs SO2The electon transfer product of formation and the H being passed through2S reaction equation:
N,N-Dimethylaniline absorbs H2The proton translocation product that S is formed and the SO being passed through2Reaction equation:
The present invention absorbs SO present in each absorbing reaction tower2Or H2S organic base-dicyandiamide solution not only can be passed through H2S Or SO2Reaction forms sulphur simple substance, but also meeting absorbent regeneration is to continue to absorb H2S and SO2, in each absorbing reaction tower Reaction and absorption process cooperation-removal H are carried out simultaneously2S or SO2, and regenerate the organic Alkali absorption H come2S or SO2It is separating Tower is pumped into SO after precipitating is separated by solid-liquid separation again2Or H2S absorbing reaction tower utilizes, and so reaches circularly removing H2S and SO2Recycle sulphur Purpose.
In addition, the organic base of the invention-dicyandiamide solution absorbs H2S or SO2The product of formation is considered as after being dissolved by the solvent It is to gaseous H2S or SO2A kind of activation so that the reaction no longer needs solid catalyst, to no longer need high temperature Condition;In addition the reaction itself is the exothermic oxidation reduction reaction that a Gibbs free energy greatly reduces so that this return in it is anti- Should be deeper compared to the extent of reaction of gas phase, condition is milder.Faster to reaction, conversion ratio is higher.
The invention has the benefit that
(1) H being passed through in the present invention2S or SO2SO is absorbed with into tower2Or H2While organic base-solvent reaction of S also Can the organic Alkali absorption that not utilized in the organic base of reaction regeneration and process, regenerated organic base and unused organic Alkali absorption H2S or SO2Next SO can be directly entered after being separated by solid-liquid separation by knockout tower2Or H2S reactive absorption tower utilizes;So Circulation technology avoids the desorption and regeneration process of organic base, efficiently solves traditional amine absorption technique desorption energy consumption height, absorbs The serious problem of agent volatilization loss.
(2) H being passed through in the method for the invention2S or SO2It can carry out reaction simultaneously in tower and absorb two processes, Make the H being passed through2S or SO2Land use systems are more, and utilization efficiency is higher, so that the removal efficiency of the technique is than traditional amine absorption technique It is higher.
(3) present invention keeps traditional gas phase claus reaction real when liquid phase is mildly not necessarily to add any catalyst It is existing, break the thermal balance limitation of gas phase claus reaction, improves H by a relatively large margin while reducing energy consumption of reaction2S conversion ratio;And And since the organic base of addition is to H2S or SO2Activation, the △ of claus reaction in additionrGm< < 0, the extent of reaction is larger, It is more quick, efficient not only to make the liquid-phase claus reaction in the system, but also works as H2S or SO2Also have when being in lower partial pressure There is good effect, without subsequent fine desulfurizing technology, greatly should to traditional gas phase claus process one kind Into.
(4) the complete removing H of tradition2S technique includes that absorption section and Crouse recycle sulphur workshop section, the method for the invention It will absorb and be carried out with the high conversion rate in individual equipment i.e. absorption tower of reacting, and not only make cumbersome traditional removing H2S technique It is simpler efficient, also it is more in line with the theory of Green Chemistry.
(5) technique of the present invention can not only be in H2S removes field application, and when a certain region exists simultaneously SO2Or H2When two kinds of exhaust gas of S, such as coal-bed gas exploitation process, the technique just can bigizationner to play it efficiently quickly recyclable simultaneously Remove H2S and SO2Advantage, while solve the problems, such as two class exhaust gas remove.
(6) H in the method for the invention2S and SO2Respectively under 0.1%~10% and 1%~10% low partial pressure, through flue gas point Analyzer analyzes H2S and SO2Removal efficiency be respectively 97.7%~99.8% and 98.4%~99.9%;Pass through note after circulation a period of time The flow and flue gas analyzer of record inlet and outlet flue gas are analyzed to obtain H2S and SO2Exit concentration be respectively 5ppm~20ppm and 300ppm~950ppm, the rate of recovery of sulphur simple substance are 96.2%~99.2%.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below with reference to concrete technology embodiment, invention is further described in detail, but protection scope of the present invention is simultaneously It is not limited to the content.
Embodiment 1
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase from H2S absorbing reaction tower top flows into, and circulation absorbs SO2Have Machine alkali-solvent meeting and H2Liquid-phase claus reaction occur for S generate sulphur simple substance simultaneously to regenerate organic base absorbent, and unemployed has Machine alkali-solvent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing is from tower top Discharge;Then H is absorbed2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through separation Tank produces sulphur simple substance from knockout drum bottom, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction Tower, organic base is n,N-Dimethylaniline in organic base-solvent, and solvent is diethylene glycol monomethyl ether, organic in organic base-solvent The mole percent content of alkali is 30%.
(2) contain the SO of 5% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower
After 30min is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 30min, H2The removal efficiency of S is 99.3%, SO2Removal efficiency be 99.4%, H2S exit concentration is 8ppm, SO2Outlet Concentration is 200ppm;It recycles in 30min, the element S rate of recovery is 98.2%.
Embodiment 2
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 5% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is n,N-Dimethylaniline in solvent, and solvent is diethylene glycol monomethyl ether, moles the hundred of organic base in organic base-solvent Fractional content is 30%.
(2) contain the SO of 5% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 40min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 40min, H2The removal efficiency of S is 98.7%, SO2Removal efficiency be 99.2%, H2S exit concentration is 12ppm, SO2Exit concentration is 313ppm;It recycles in 40min, the element S rate of recovery is 97.6%.
Embodiment 3
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is n,N-Dimethylaniline in solvent, and solvent is sulfolane, the mole percent content of organic base in organic base-solvent It is 60%.
(2) contain the SO of 15% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 60min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 60min, H2The removal efficiency of S is 98.5%, SO2Removal efficiency be 98.7%, H2S exit concentration is 15ppm, SO2Exit concentration is 360ppm;It recycles in 60min, the element S rate of recovery is 97.3%.
Embodiment 4
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is tetramethylguanidine in alkali-solvent, and solvent is diethylene glycol monomethyl ether, the Mole percent of organic base in organic base-solvent Number content is 30%.
(2) contain the SO of 1% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 3h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 3h, H2The removal efficiency of S is 97.7%, SO2Removal efficiency be 98.4, H2S exit concentration is 20ppm, SO2It exports dense Degree is 950ppm;It recycles in 3h, the element S rate of recovery is 96.2%.
Embodiment 5
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is N in solvent, and N- dimethyl cyclohexyl amine, solvent is water, and the mole percent content of organic base is in organic base-solvent 75%。
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 1h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 1h, H2The removal efficiency of S is 98.8%, SO2Removal efficiency be 99.0%, H2S exit concentration is 10ppm, SO2It exports dense Degree is 505ppm;It recycles in 1h, the element S rate of recovery is 97.9%.
Embodiment 6
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is methylphenylamine in alkali-solvent, and solvent is diethylene glycol monomethyl ether, moles the hundred of organic base in organic base-solvent Fractional content is 50%.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 50min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 50min, H2The removal efficiency of S is 99.4%, SO2Removal efficiency be 99.6%, H2S exit concentration is 7ppm, SO2 Exit concentration is 400ppm;It recycles in 50min, the element S rate of recovery is 98.9%.
Embodiment 7
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is 3- pyridinemethanol in solvent, and solvent is ethyl alcohol, and the mole percent content of organic base is 75% in organic base-solvent.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 1h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 1h, H2The removal efficiency of S is 99.6%, SO2Removal efficiency be 99.3%, H2S exit concentration is 6ppm, SO2It exports dense Degree is 425ppm;It recycles in 1h, the element S rate of recovery is 99.0%.
Embodiment 8
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 10% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is 3- pyridinemethanol in alkali-solvent, and solvent is ethyl alcohol, and the mole percent content of organic base is in organic base-solvent 60%。
(2) contain the SO of 15% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 30min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 30min, H2The removal efficiency of S is 99.8%, SO2Removal efficiency be 99.7%, H2S exit concentration is 5ppm, SO2 Exit concentration is 345ppm;It recycles in 50min, the element S rate of recovery is 99.2%.
Embodiment 9
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 10% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is 3- pyridinemethanol in alkali-solvent, and solvent is ethyl alcohol, and the mole percent content of organic base is in organic base-solvent 60%。
(2) contain the SO of 1% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 3h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 3h, H2The removal efficiency of S is 98.7%, SO2Removal efficiency be 99.9%, H2S exit concentration is 19ppm, SO2It exports dense Degree is 300ppm;It recycles in 3h, the element S rate of recovery is 97.4%.
Embodiment 10
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is tetramethylguanidine in alkali-solvent, and solvent is N- methyl pyrrolidone, the Mole percent of organic base in organic base-solvent Number content is 30%.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 1h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 1h, H2The removal efficiency of S is 98.2%, SO2Removal efficiency be 98.9%, H2S exit concentration is 10ppm, SO2It exports dense Degree is 370ppm;It recycles in 1h, the element S rate of recovery is 97.2%.
Embodiment 11
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is cyclohexylamine in alkali-solvent, and solvent is water, and the mole percent content of organic base is 75% in organic base-solvent.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 30min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 30min, H2The removal efficiency of S is 98.6%, SO2Removal efficiency be 99.3%, H2S exit concentration is 9ppm, SO2 Exit concentration is 328ppm;It recycles in 30min, the element S rate of recovery is 97.4%.
Embodiment 12
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is 1,8- diazabicylo, 11 carbon -7- alkene (DBU) in alkali-solvent, and solvent is ethyl alcohol, organic in organic base-solvent The mole percent content of alkali is 50%.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 30min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 30min, H2The removal efficiency of S is 99.5%, SO2Removal efficiency be 99.2%, H2S exit concentration is 6ppm, SO2 Exit concentration is 381ppm;It recycles in 30min, the element S rate of recovery is 98.9%.
Embodiment 13
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 5% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is dimethylethanolamine in solvent, and solvent is N- methyl pyrrolidone, the Mole percent of organic base in organic base-solvent Number content is 50%.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 10min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 10min, H2The removal efficiency of S is 99.6%, SO2Removal efficiency be 99.1%, H2S exit concentration is 8ppm, SO2 Exit concentration is 394ppm;It recycles in 10min, the element S rate of recovery is 99.0%.
Embodiment 14
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 0.1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from rear Continuous process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-it is molten Agent meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-is molten Agent and the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.So After absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from point Sulphur simple substance is produced from pot bottom, H will be absorbed from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, it is organic Organic base is diisopropanolamine (DIPA) in alkali-solvent, and solvent is diethylene glycol monomethyl ether, moles the hundred of organic base in organic base-solvent Fractional content is 40%.
(2) contain the SO of 10% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 2h is recycled, scored by the flue gas analyzer and flow of the molal quantity and import and export that obtain sulphur simple substance Analysis, after recycling 2h, H2The removal efficiency of S is 97.9%, SO2Removal efficiency be 98.7%, H2S exit concentration is 19ppm, SO2It exports dense Degree is 880ppm;It recycles in 2h, the element S rate of recovery is 96.5%.
Embodiment 15
It is a kind of to utilize the energy-efficient recyclable removing H of liquid phase Crouse2S and SO2The process of sulphur is recycled, detailed process is such as Under:
(1) contain the H of 1% atm2S exhaust gas is from H2S absorbing reaction tower bottom is passed through, the liquid phase of organic base-solvent composition and from subsequent Process cycles absorb SO2Organic base-solvent liquid phase flowed into from the tower top, circulation absorbs SO2Organic base-solvent Meeting and H2S occurs liquid-phase claus reaction and generates sulphur simple substance and regenerate organic base absorbent, and unemployed organic base-solvent And the regenerated organic base of liquid-phase claus reaction can also absorb the H being passed through2S, exhaust gas after processing are discharged from tower top.Then Absorb H2S and organic base-solvent solid-liquid two-phase system containing sulphur simple substance are from H2S absorb the bottom of the tower is passed through knockout drum, from separation Pot bottom produces sulphur simple substance, will absorb H from knockout drum top2Organic base-solvent of S is pumped into SO2Absorbing reaction tower, organic base- Organic base is n,N-Dimethylaniline in solvent, and solvent is water, and the mole percent content of organic base is in organic base-solvent 45%。
(2) contain the SO of 15% atm2Exhaust gas is passed through SO from bottom2Absorbing reaction tower equally absorbs H in the tower2S's is organic Alkali-solvent and the SO being passed through2Liquid-phase claus reaction occurs to generate sulphur simple substance and regenerate organic base, regenerated organic base and original Carry out the unused organic base of system and also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain The organic base of sulphur simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, SO will be finally absorbed again2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower.
After 40min is recycled, by obtaining the molal quantity of sulphur simple substance and the flue gas analyzer and flow of import and export Meter analysis, after recycling 40min, H2The removal efficiency of S is 99.6%, SO2Removal efficiency be 98.9%, H2S exit concentration is 7ppm, SO2 Exit concentration is 688ppm;It recycles in 40min, the element S rate of recovery is 98.6%.

Claims (5)

1. a kind of circularly removing H2S and SO2And the method for recycling sulphur, which is characterized in that specifically includes the following steps:
(1) contain H2The industrial waste gas of S is from H2S absorbing reaction tower bottom is passed through, organic base-solvent and from subsequent technique be circulated throughout come Absorb SO2Organic base-solvent from H2S absorbing reaction tower top flows into, and absorbs SO2Organic base-solvent and H2S occurs Liquid-phase claus reaction generates sulphur simple substance and regenerates organic base absorbent, and unused organic base-solvent and liquid phase Crouse The organic base of reaction regeneration can also absorb the H being passed through2S, exhaust gas after processing is arranged from tower top, from H2S absorbing reaction tower bottom row Reaction solution out is passed through in knockout drum, produces sulphur simple substance from knockout drum bottom, will absorb H from knockout drum top2S's is organic Alkali-solvent is passed through SO2Absorbing reaction tower;
(2) contain SO2Industrial waste gas be passed through SO from bottom2Absorbing reaction tower, in SO2H is absorbed in absorbing reaction tower2The organic base-of S Solvent and the SO being passed through2It liquid-phase claus reaction occurs generates sulphur simple substance simultaneously to regenerate organic base, regenerated organic base and original The unused organic base of system also can absorb SO2, exhaust gas after treatment is discharged from the tower top, and absorbs SO2And contain sulphur The organic base of simple substance-solvent liquid phase system is from SO2Absorb the bottom of the tower is passed through knockout drum, produces sulphur simple substance from knockout drum bottom, most SO will be absorbed again afterwards2Organic base-solvent be pumped into H at the top of the knockout drum2S absorbing reaction tower realizes that circular response absorbed Journey.
2. circularly removing H according to claim 12S and SO2And the method for recycling sulphur, it is characterised in that: H in step (1)2S Partial pressure is 0.1%~10% atm.
3. circularly removing H according to claim 12S and SO2And the method for recycling sulphur, it is characterised in that: in organic base-solvent Organic base are as follows: tetramethylguanidine, 3- pyridinemethanol, cyclohexylamine, N-methylcyclohexylamine, N, N- dimethyl cyclohexyl amine, N, N- diformazan One of base aniline, 1,8- diazabicylo, 11 carbon -7- alkene (DBU), dimethylethanolamine, diisopropanolamine (DIPA), solvent is One of sulfolane, diethylene glycol monomethyl ether, ethyl alcohol, water, N-Methyl pyrrolidone.
4. circularly removing H according to claim 32S and SO2And the method for recycling sulphur, it is characterised in that: in organic base-solvent Organic base molar content be 30%~75%.
5. circularly removing H according to claim 32S and SO2And the method for recycling sulphur, it is characterised in that: step (2) SO2Point Pressure is 1%~15% atm.
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