CN110172365A - The removal methods of the preparation of hydrogen sulfide absorption liquid, regeneration method and hydrogen sulfide - Google Patents
The removal methods of the preparation of hydrogen sulfide absorption liquid, regeneration method and hydrogen sulfide Download PDFInfo
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- CN110172365A CN110172365A CN201910517003.5A CN201910517003A CN110172365A CN 110172365 A CN110172365 A CN 110172365A CN 201910517003 A CN201910517003 A CN 201910517003A CN 110172365 A CN110172365 A CN 110172365A
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- hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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Abstract
The invention discloses the removal methods of a kind of preparation of hydrogen sulfide absorption liquid, regeneration method and hydrogen sulfide, the preparation method of hydrogen sulfide absorption liquid, eutectic solvent is prepared after including the following steps: quaternary ammonium salt hydrogen acceptor and the heating reaction of amides hydrogen donor, eutectic solvent is compounded with the compound oxidant containing trivalent iron salt is prepared the eutectic solvent containing oxidant to get hydrogen sulfide absorption liquid.It can be elemental sulfur by Oxidation of Hydrogen Sulfide that this, which contains the ferric iron in the eutectic solvent of oxidant, and then hydrogen sulfide is removed.The hydrogen sulfide absorption liquid is big to the absorptive capacity of hydrogen sulfide, and the preparation of absorbing liquid is simple, low in raw material price.
Description
Technical field
The invention belongs to technical field of chemical separation, and in particular to a kind of preparation of hydrogen sulfide absorption liquid, regeneration method and
The removal methods of hydrogen sulfide, for removing hydrogen sulfide in producing synthesis gas from coal.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
It synthesizing in ammonia Chemical Manufacture, the source of unstripped gas is producing synthesis gas from coal, during coal gasification, the sulphur that contains in coal
Element can largely enter synthesis gas in the form of hydrogen sulfide, and in the reaction that synthesis gas prepares urea, the presence of hydrogen sulfide is not
Personal safety is only made to generate hidden danger, and the hydrogen sulfide in industrial production can also cause the corrosion of metallic conduit and device, more
Making Chemical Manufacture operator unacceptable, there are also vulcanization Hydrogen Energies to cause catalyst poisoning, further will affect intermediate products and most
The quality of finished product, it is therefore desirable to by hydrogen sulfide stripping.Hydrogen sulfide is inflammable and explosive, and the combustion decomposition product of hydrogen sulfide is titanium dioxide
Sulphur.No matter being discharged after hydrogen sulfide direct emission or burning, atmospheric environment can all be impacted.Therefore, whether from ring
The angle or industrial angle of border protection all must carry out removing purification to hydrogen sulfide.
Currently, there are many technology for the removing hydrogen sulfide industrially applied, have their own characteristics each.The method root of tradition removing hydrogen sulfide
Removing Hydrogen Sulfide by Dry Process and wet process removing hydrogen sulfide two major classes can be classified as according to the physical aspect of desulfurizing agent.Desulfurization used now
Method there is also: higher cost, the desulfurizer occupied area of some desulfurizing agents are larger, and desulfurizing agent cannot regenerate so that need
Often replacement desulfurizing agent, cannot recycle, so that the higher cost of removing hydrogen sulfide, the doctor solution of some generations all have one
Fixed toxicity, liquid waste disposal technique is immature, so that industrial application is restricted, be easy to cause the secondary pollution to environment;
The problems such as tower is easily blocked up in some presence, sulfur recovery rate is low, energy consumption is high, operating cost is high, some doctor solution stability is bad, industry
In be frequently necessary to using the continual addition manner of twenty four hours, and the pH value of doctor solution needs to be maintained between 8-10,
Just be conducive to the performance of catalyst.The more mainly ionic liquid for being used to remove hydrogen sulfide of nearest experimental study, from
Sub- liquid has the advantages that certain: saturated vapor pressure is smaller, lower fusing point, good stability, and type is mostly etc..But inventor
It was found that there is also some defects for most of ionic liquids in real industrial application: most of functionalized ion liquid preparation process
It is complex, it needs two steps or multistep to synthesize more, needs further to purify after synthesis, and purification difficult.Accordingly, with respect to
For traditional organic solvent, ionic liquid preparation complexity, higher cost.This is to limit ionic liquid in the industrial production at present
The main reason of large-scale application;The biocompatibility of most of ionic liquids is poor, has to human body and aquatic organism
Potential cytotoxicity, raw materials used price are more expensive etc..
Summary of the invention
For above-mentioned the technical problems existing in the prior art, the object of the present invention is to provide a kind of hydrogen sulfide absorption liquid
The removal methods of preparation, regeneration method and hydrogen sulfide.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of preparation method of hydrogen sulfide absorption liquid, includes the following steps:
Be prepared eutectic solvent after quaternary ammonium salt hydrogen acceptor and the heating reaction of amides hydrogen donor, eutectic solvent with
The eutectic solvent containing oxidant is prepared to get hydrogen sulfide absorption liquid in compound oxidant compounding containing trivalent iron salt.
Trivalent iron salt directly carries out oxidative absorption to hydrogen sulfide, is the wet oxidation method carried out, needs certain solvent
Oxidation reaction could more adequately be occurred into for molysite after hydrogen sulfide absorption, ferric salt solution has the absorption of hydrogen sulfide
Limit, and it is influenced by environmental temperature, cause hydrogen sulfide that cannot be oxidized completely, and the solvent of solution itself is readily volatilized, damages
It loses larger, needs largely to supplement.
The effect of eutectic solvent is exactly as the absorbent for absorbing hydrogen sulfide.Hydrogen sulfide is in the mistake by this absorbent
The polarity of Cheng Zhong, eutectic agent are larger, carry out physical absorption, selective absorption performance to hydrogen sulfide using the effect of itself hydrogen bond
Good, larger to the absorptive capacity of hydrogen sulfide, experiment shows that the absorptive capacity to hydrogen sulfide up to 3.2mol/kg, enables oxidant
It comes into full contact with and is reacted to easier that the hydrogen sulfide stripping of absorption is clean with hydrogen sulfide, and the steam of eutectic solvent
Press small, few to volatilize, the loss of solvent is less, and magnitude of recruitment is seldom in entire reaction process, can regenerate and be recycled for multiple times.
It can be elemental sulfur by Oxidation of Hydrogen Sulfide that this, which contains the ferric iron in the eutectic solvent of oxidant, and then will vulcanization
Hydrogen removes.The hydrogen sulfide absorption liquid is big to the absorptive capacity of hydrogen sulfide, and the preparation of absorbing liquid is simple, low in raw material price.
In some embodiments, the quaternary ammonium salt hydrogen acceptor is tetrabutylammonium bromide or tetrabutylammonium chloride, the acyl
Amine hydrogen donor is urea.
In some embodiments, the molar ratio of the quaternary ammonium salt hydrogen acceptor and amides hydrogen donor is 1:1-3.
In some embodiments, the temperature of the heating reaction is 130-140 DEG C.
A kind of removal methods of hydrogen sulfide, include the following steps:
Producing synthesis gas from coal is passed through in the hydrogen sulfide absorption liquid, the ferric iron in hydrogen sulfide absorption liquid will vulcanize hydrogen reduction
For elemental sulfur, the removing of hydrogen sulfide is realized.
In some embodiments, in the absorption process of hydrogen sulfide, further include the steps that stirring absorbing liquid.It is absorbed by stirring
Liquid comes into full contact with absorbing liquid with hydrogen sulfide, and then hydrogen sulfide is completely removed.
In some embodiments, further include the steps that for the elemental sulfur of generation being filtered to remove.
The regeneration method of the hydrogen sulfide absorption liquid, includes the following steps:
After the absorbing liquid for absorbing hydrogen sulfide is filtered to remove sulphur simple substance, oxidant is added into absorbing liquid, it will be in absorbing liquid
Ferrous ions be ferric ion, the hydrogen sulfide absorption liquid after being regenerated.
In some embodiments, the oxidant is air or/and hydrogen peroxide.
In some embodiments, when the oxidant is hydrogen peroxide, the additional amount of hydrogen peroxide is the quality of absorbing liquid
0.01-0.05%.
Advantageous effects of the invention are as follows:
1, the present invention prepares the eutectic solvent of green, one of former material using raw material that are cheap, being easy to get
Material can also be factory itself product, reduction production cost easy to industrialized production.
2, eutectic agent absorption hydrogen sulfide capacity is larger, can preferably absorb hydrogen sulfide, under the action of oxidant, generates
Elemental sulfur to form elemental sulfur byproduct by filtering and drying, more conducively transport, or the raw material as other products.
3, make eutectic solvent that can recycle benefit with rapid regeneration by way of a certain amount of hydrogen peroxide is added or is passed through air
With regeneration is simple, reduces production cost, while reducing environmental pollution.
4, the H2S SCAVENGER prepared can realize that seamless interfacing is replaced in existing production sulfur removal technology, not have to existing
There is production process equipment to carry out big change, reduce investment, reduces process equipment and change generated risk.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Embodiment 1
1) prepared by hydrogen sulfide absorption liquid
Tetrabutylammonium bromide is added into the three neck round bottom flask of 500ml: urea (molar ratio 1:2) passes through mechanical stirring
It is heated to 135 DEG C in oil bath pan, obtains colorless and transparent, the preferable liquid of mobility, it is slightly cooling, add 3% tri-chlorination
Iron is obtained by stirring containing ferric compounding eutectic solvent, static to be cooled to room temperature.
2) removing of hydrogen sulfide
Producing synthesis gas from coal is passed through rate by pipeline control to be passed through in a certain amount of hydrogen sulfide absorption liquid, in bottom magnetic force
It is absorbed hydrogen sulfide under stirring, internal liquid convection current is made by stirring, hydrogen sulfide is reduced to list under the action of oxidant
Internal elemental sulfur is filtered to remove by matter sulphur, the absorbing liquid after reaction by filter device.The adsorbance for measuring hydrogen sulfide is
2.8mol/kg。
3) recycling utilization of absorbing liquid
The hydrogen peroxide of air and addition 0.02% is passed through in the absorbing liquid of removing hydrogen sulfide, under dual oxidation,
Absorbing liquid is set to regenerate recycling.
Embodiment 2
1) prepared by hydrogen sulfide absorption liquid
Tetrabutylammonium bromide is added into the three neck round bottom flask of 500ml: urea (molar ratio 1:1) passes through mechanical stirring
It is heated to 135 DEG C in oil bath pan, obtains colorless and transparent, the preferable liquid of mobility, it is slightly cooling, add 5% tri-chlorination
Iron is obtained by stirring containing ferric compounding eutectic solvent, static to be cooled to room temperature.
2) removing of hydrogen sulfide
Producing synthesis gas from coal is passed through rate by pipeline control to be passed through in a certain amount of hydrogen sulfide absorption liquid, in bottom magnetic force
It is absorbed hydrogen sulfide under stirring, internal liquid convection current is made by stirring, hydrogen sulfide is reduced to list under the action of oxidant
Internal elemental sulfur is filtered to remove by matter sulphur, the absorbing liquid after reaction by filter device.The adsorbance for measuring hydrogen sulfide is
3.2mol/kg。
3) recycling utilization of absorbing liquid
Being passed through air in the absorbing liquid of removing hydrogen sulfide and 0.04% hydrogen peroxide is added makes under dual oxidation
Absorbing liquid can regenerate recycling.
Embodiment 3
1) prepared by hydrogen sulfide absorption liquid
Tetrabutylammonium chloride is added into the three neck round bottom flask of 500ml: urea (molar ratio 1:2) passes through mechanical stirring
It is heated to 140 DEG C in oil bath pan, obtains colorless and transparent, the preferable liquid of mobility, it is slightly cooling, add 3% tri-chlorination
Iron is obtained by stirring containing ferric compounding eutectic solvent, static to be cooled to room temperature.
2) removing of hydrogen sulfide
Producing synthesis gas from coal is passed through rate by pipeline control to be passed through in hydrogen sulfide absorption liquid, is made under the magnetic agitation of bottom
Hydrogen sulfide is absorbed, and makes internal liquid convection current by stirring, hydrogen sulfide is reduced to elemental sulfur under the action of oxidant, react
Internal elemental sulfur is filtered to remove by absorbing liquid afterwards by filter device.The adsorbance for measuring hydrogen sulfide is 3.1mol/kg.
3) recycling utilization of absorbing liquid
Being passed through air in the absorbing liquid of removing hydrogen sulfide allows absorbing liquid to regenerate recycling.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of hydrogen sulfide absorption liquid, characterized by the following steps:
Be prepared eutectic solvent after quaternary ammonium salt hydrogen acceptor and the heating reaction of amides hydrogen donor, eutectic solvent with contain
The eutectic solvent containing oxidant is prepared to get hydrogen sulfide absorption liquid in the compound oxidant compounding of trivalent iron salt.
2. the preparation method of hydrogen sulfide absorption liquid according to claim 1, it is characterised in that: the quaternary ammonium salt hydrogen acceptor
For tetrabutylammonium bromide or tetrabutylammonium chloride, the amides hydrogen donor is urea.
3. the preparation method of hydrogen sulfide absorption liquid according to claim 1, it is characterised in that: the quaternary ammonium salt hydrogen acceptor
Molar ratio with amides hydrogen donor is 1:1-3.
4. the preparation method of hydrogen sulfide absorption liquid according to claim 1, it is characterised in that: the temperature of the heating reaction
It is 130-140 DEG C.
5. a kind of removal methods of hydrogen sulfide, characterized by the following steps:
Producing synthesis gas from coal is passed through in any hydrogen sulfide absorption liquid of claim 1-4, the ferric iron in hydrogen sulfide absorption liquid
Hydrogen sulfide is reduced to elemental sulfur, realizes the removing of hydrogen sulfide.
6. the removal methods of hydrogen sulfide according to claim 5, it is characterised in that: in the absorption process of hydrogen sulfide, also wrap
The step of including stirring absorbing liquid.
7. the removal methods of hydrogen sulfide according to claim 5, it is characterised in that: further include the elemental sulfur filtering that will be generated
The step of removing.
8. the regeneration method of any hydrogen sulfide absorption liquid of claim 1-4, characterized by the following steps:
After the absorbing liquid for absorbing hydrogen sulfide is filtered to remove sulphur simple substance, oxidant is added into absorbing liquid, by the Asia in absorbing liquid
Ferrous ions oxidation is ferric ion, the hydrogen sulfide absorption liquid after being regenerated.
9. the regeneration method of hydrogen sulfide absorption liquid according to claim 7, it is characterised in that: the oxidant is air
Or/and hydrogen peroxide.
10. the regeneration method of hydrogen sulfide absorption liquid according to claim 9, it is characterised in that: the oxidant is dioxygen
When water, the additional amount of hydrogen peroxide is the 0.01-0.05% of the quality of absorbing liquid.
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Citations (5)
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CN101601961A (en) * | 2009-07-01 | 2009-12-16 | 河北科技大学 | Absorb SO with halogenated alkyl quaternary ammonium salt ionic liquid 2The method of gas |
CN102020248A (en) * | 2009-09-16 | 2011-04-20 | 北京化工大学 | Method for non-aqueous phase wet oxidation of hydrogen sulfide |
US20130118955A1 (en) * | 2008-05-26 | 2013-05-16 | Instituto Mexicano Del Petroleo | Desulfurization of hydrocarbons by ionic liquids and preparation of ionic liquids |
CN106366005A (en) * | 2016-08-08 | 2017-02-01 | 河南工业大学 | Method for preparing eutectic solvent through ball milling |
CN108840311A (en) * | 2018-06-22 | 2018-11-20 | 南京大学 | It is a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium |
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2019
- 2019-06-14 CN CN201910517003.5A patent/CN110172365A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20130118955A1 (en) * | 2008-05-26 | 2013-05-16 | Instituto Mexicano Del Petroleo | Desulfurization of hydrocarbons by ionic liquids and preparation of ionic liquids |
CN101601961A (en) * | 2009-07-01 | 2009-12-16 | 河北科技大学 | Absorb SO with halogenated alkyl quaternary ammonium salt ionic liquid 2The method of gas |
CN102020248A (en) * | 2009-09-16 | 2011-04-20 | 北京化工大学 | Method for non-aqueous phase wet oxidation of hydrogen sulfide |
CN106366005A (en) * | 2016-08-08 | 2017-02-01 | 河南工业大学 | Method for preparing eutectic solvent through ball milling |
CN108840311A (en) * | 2018-06-22 | 2018-11-20 | 南京大学 | It is a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium |
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