CN109603455A - A kind of absorbent and method removing hydrogen sulfide in methane - Google Patents
A kind of absorbent and method removing hydrogen sulfide in methane Download PDFInfo
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- CN109603455A CN109603455A CN201910079906.XA CN201910079906A CN109603455A CN 109603455 A CN109603455 A CN 109603455A CN 201910079906 A CN201910079906 A CN 201910079906A CN 109603455 A CN109603455 A CN 109603455A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention provides a kind of absorbents for removing hydrogen sulfide in methane, the absorbent is aqueous solution, solute includes Complexing Iron and complexing ferrous iron, N, N- dihydroxyalkyl piperazine, sodium carbonate and sodium bicarbonate buffer system, nonionic surface active agent, ionic surfactant and antioxidant；Wherein, the concentration of ferro element is 100~2000mg/L, the molar ratio of Complexing Iron and complexing ferrous iron is 0.2~5, pH value of solution is controlled 6.0~9.0 by sodium carbonate and sodium bicarbonate buffer system, the concentration of nonionic surface active agent is 50~500mg/L, and the concentration of ionic surfactant is 10~100mg/L, N, the concentration of N- dihydroxy ethyl piperazine is 10~100mg/L, and the concentration of antioxidant is 50~500mg/L.The present invention also provides the methods for using absorbent removing hydrogen sulfide.
Description
Technical field
The present invention relates to gas purification technique field, especially a kind of absorbent and method for removing hydrogen sulfide in methane.
Background technique
Biogas be the organic substances such as agricultural crop straw, livestock and poultry feces, kitchen garbage under anaerobic, by microorganism
A kind of mixed gas that fermentation generates, the main component of biogas are methane and carbon dioxide, also contain a small amount of nitrogen, oxygen
The ingredients such as gas, hydrogen and hydrogen sulfide.The utilization of biogas with generate electricity with refining natural gas based on, had become as renewable energy
The important component of China's energy strategy.Hydrogen sulfide have corrosivity, and burn utilize during can be converted into dioxy
Change sulphur, being discharged into atmosphere will form sour gas pollution, seriously affect environment.Therefore, it is needed before marsh gas power generation or purification pair
Biogas is purified, and hydrogen sulfide gas therein is removed.
Classify according to the removing principle of hydrogen sulfide, physical method removing hydrogen sulfide, chemical method removing vulcanization can be divided into
Hydrogen and bioanalysis remove hydrogen sulfide.Physical method removing hydrogen sulfide can be divided into using active carbon, molecular sieve as the absorption method of representative
With using organic alcohols as the physical solvent process of representative；Chemical method can be divided into using iron oxide as the dry method of representative and with hydroxide
Sodium and chlor-alkali mixed liquor, the wet process that Complexing Iron is representative；Bioanalysis can be divided into acid system biological desulphurization and alkaline process biological desulphurization.
Wherein, dry method and absorption method desulfurization contain lower concentration of hydrogen sulfide, the fine de-sulfur being chiefly used in after wet process suitable for gas
Change hydrogen；Acid system and alkaline process biological desulphurization are related to the culture of microorganism, and the debugging cycle of device is longer during engineer application, phase
Than under, most promising is wet chemical removing hydrogen sulfide technology.
Chinese patent CN104492251A discloses a kind of microorganism catalysis regeneration method of Complexing Iron, which utilizes micro-
The catalytic action of biology, accelerates the oxidation regeneration of Complexing Iron.Used complexing agent includes ethylenediamine tetra-acetic acid (EDTA), sulfo group
Salicylic acid (FD), triethanolamine (TEA), nitrilotriacetic acid (NTA), citric acid (CA) etc., due to the network of FD, NTA, CA and iron
It is unstable in the middle high section pH to close object, easily forms precipitating, it is therefore preferable that pH value is 1.5 to 2.5.But in this pH range
Under, compared to neutral and alkali, absorbent is remarkably decreased the washing effect of hydrogen sulfide in gas phase, when needing to greatly improve gas-liquid washing
Liquid-gas ratio can be only achieved preferable washing effect, which results in significantly rising for system energy consumption.Simultaneously as ligand is mostly small
Molecular organic has preferable biocompatibility, and the presence of microorganism will lead to the biodegrade of ligand, so that absorbent
Magnitude of recruitment greatly improves.
Chinese patent CN102151476A discloses a kind of method of removing hydrogen sulfide in gas phase through oxidization under high gravity field, institute
The mixed solution used is made of Complexing Iron, alkali, sulfur modifier, defoaming agent, and wherein Complexing Iron is by EDTA, alkyl alcoholamine, iron
Salt, sodium citrate salt composition.Due to adjusting pH using small molecular alcohol amine organic base, and these existing organic bases are in its operation
Salt cannot be acidified into the range of pH 8.0-9.2 completely, also there is comparable volatility, therefore in the same of removing hydrogen sulfide
When will cause in biogas carrying part alkyl alcoholamine, always form nitrogen oxides secondary pollution in combustion process later.Another party
The molar ratio of face, used ligand and iron is excessively high, is 1.4-5, excessive ligand is when elemental sulfur is separated by solid-liquid separation by solid
Sulfur granules take system out of, can not be recycled, this can greatly increase the operating cost of system.
Chinese patent CN107511045A discloses a kind of method for removing hydrogen sulfide in gas, involves filler using power
Tower, and the removing of this device technique hydrogen sulfide mostly suitable for raw material of industry gas need to carry out chilling using power wave apparatus
And it is pre- de-, it reuses packed tower and smart removing, unstripped gas temperature and pressure with higher is carried out to hydrogen sulfide.The temperature of biogas and
Pressure is not high, and biogas boosts according to above-mentioned process requirement, generates excessive energy consumption, therefore this technique is removed in biogas
Hydrogen sulfide domain variability is not applicable.
To sum up, it needs to develop and is suitable for wider concentration of hydrogen sulfide range, is easy to debug, the biogas of stability and high efficiency removing sulphur
Change hydrogen technology.
Summary of the invention
The object of the present invention is to provide one kind to be suitable under normal temperature and pressure conditions, efficient stable, driving and parking is flexible, debugging is all
The technology for the removing hydrogen sulfide in methane that phase is short, energy consumption and material consumption are low, including absorbent and the method for removing hydrogen sulfide using it.
To achieve the above object, in a first aspect, the present invention provide it is a kind of for removing the absorbent of hydrogen sulfide in methane, institute
Stating absorbent is aqueous solution, and solute includes that Complexing Iron and complexing ferrous iron, N, N- dihydroxyalkyl piperazine, sodium carbonate and sodium bicarbonate are slow
Rush system, nonionic surface active agent, ionic surfactant and antioxidant；Wherein, the concentration of ferro element be 100~
The molar ratio of 2000mg/L, Complexing Iron and complexing ferrous iron is 0.2~5, is controlled by sodium carbonate and sodium bicarbonate buffer system molten
Liquid pH is 6.0~9.0, and the concentration of nonionic surface active agent is 50~500mg/L, and the concentration of ionic surfactant is
The concentration of 10~100mg/L, N, N- dihydroxy ethyl piperazine is 10~100mg/L, and the concentration of antioxidant is 50~500mg/L.
Further, the complexing ligand of the Complexing Iron and complexing ferrous iron is alkyl diamine tetraacethyl, ethoxy alkyl two
One or more of amine triacetic acid and dihydroxy ethyl alkyl diamine oxalic acid.
Further, alkyl described in the N, N- dihydroxyalkyl piperazine is ethylidene or propylidene.
Further, the N, N- dihydroxyalkyl piperazine are N, in N- dihydroxy ethyl piperazine and N, N- dihydroxypropyl piperazine
It is one or two kinds of.
Further, the sodium carbonate-bicarbonate buffer system includes the one or two of sodium carbonate and sodium bicarbonate.
Further, the nonionic surface active agent include octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether,
One or more of dodecanol polyoxyethylene ether；
Further, the ionic surfactant includes neopelex, triethyl group dodecyl chlorination
One or more of ammonium, tributyl octyl ammonium chloride, tetrabutylammonium bromide and dodecyl benzyl dimethyl ammonium chloride.
Further, the antioxidant include polypropylene oxide, hydroquinone, tert-butylhydroquinone, sodium sulfite,
One or more of sodium thiosulfate, polyethylene glycol and dibutyl hydroxy toluene.
Second aspect, the embodiment of the present invention provide a kind of side of removing hydrogen sulfide in methane using above-mentioned absorbent
Method, the equipment that the method uses include spray absorber, sedimentation and regenerating tank, lean pump, discharge pump, oxidation fan and solid-liquid
Separative unit；The described method includes:
The bottom on absorption tower sucks biogas, and biogas connects with from the absorbent lean solution counter current contacting under top spraying layer spray
Absorbent after touch forms rich solution, collects in absorb the bottom of the tower, sedimentation regenerating tank is flowed automatically to by gravity, after spray washing
Biogas in hydrogen sulfide be removed, purification system is left by tower top pipeline.
Compared with prior art, of the invention to have the following beneficial effects: that (1) is suitable in rich carbonated biogas
Middle removing hydrogen sulfide；(2) unique absorbent formula designs so that absorbent is easy in use by the vulcanization in gas phase
Hydrogen is absorbed into liquid phase and the sulphur of negative divalent is efficiently oxidized to elemental sulfur, organo-mineral complexing antioxidant and bacteriostatic agent
It uses so that absorbent has long-time stability；(3) especially suitable with the matching used hydrogen sulphide removal unit of absorbent and method
Marsh gas purifying for wider concentration of hydrogen sulfide range, low gas phase temperature and pressure.
Detailed description of the invention
Fig. 1 removes the flow chart of the method for hydrogen sulfide in methane using absorbent provided in an embodiment of the present invention.
Specific embodiment
Several illustrative embodiments shown in below with reference to the accompanying drawings describe the principle and spirit of the invention.It should
Understand, describe these embodiments just for the sake of make those skilled in the art can better understand that in turn realize the present invention,
And this scope of the present invention is not limited in any way.
Provided in an embodiment of the present invention a kind of for removing the absorbent of hydrogen sulfide in methane, the absorbent is water-soluble
Liquid, solute ions include Complexing Iron and complexing is ferrous, N, N- dihydroxyalkyl piperazine, sodium carbonate and sodium bicarbonate buffer system, non-
Ionic surfactant, ionic surfactant, antioxidant.Wherein, the concentration of ferro element is in 100~2000mg/L,
The molar ratio of Complexing Iron and complexing ferrous iron controls in the range of 0.2~5, passes through sodium carbonate and sodium bicarbonate buffer system controls
PH value of solution is 6.0~9.0, and the concentration of nonionic surface active agent is in 50~500mg/L, the concentration of ionic surfactant
In 10~100mg/L, N, the concentration of N- dihydroxy ethyl piperazine is in 10~100mg/L, and the concentration of antioxidant is in 50~500mg/
L。
Wherein, complexing ligand is selected from alkyl diamine tetraacethyl, ethoxy alkyl diamine triacetic acid, dihydroxy ethyl alkyl diamine
One or more of oxalic acid, the alkyl are ethylidene or propylidene；N, N- dihydroxyalkyl piperazine are selected from N, N- dihydroxy second
Base piperazine or N, the one or two of N- dihydroxypropyl piperazine；The sodium carbonate-bicarbonate buffer system include sodium carbonate or
The one or two of sodium bicarbonate；The nonionic surface active agent includes octyl phenol polyoxyethylene ether, polyoxyethylene nonyl phenyl second
One or more of alkene ether, dodecyl polyoxyethylene ether；The ionic surfactant includes dodecyl benzene sulfonic acid
Sodium, triethyl group lauryl ammonium chloride, tributyl octyl ammonium chloride, tetrabutylammonium bromide, dodecyl dimethyl Benzylmagnesium chloride
One or more of ammonium；The antioxidant include polypropylene oxide, hydroquinone, tert-butylhydroquinone, sodium sulfite,
One or more of sodium thiosulfate, polyethylene glycol, dibutyl hydroxy toluene.
Hydrogen sulfide belongs to sour gas, is dissolved into water by gas phase and is divided into two steps, and first step is physical dissolution,
Second step be dissolved hydrogen sulfide with dissolve in alkali react.First step and the quality percentage of water in absorbent contain
Measure related, the content of water is higher, and solubility is bigger, and second step is related with the pH value of dissolution, and pH value is higher, and reaction efficiency is got over
Height, absorbent are also bigger to the ability of hydrogen sulfide absorption.The pH value of absorbent solution, which receives two factors, to be influenced, and one is vulcanization
The absorption of hydrogen will lead to absorbent acidification, the other is solution of the carbon dioxide contained in biogas in absorbent, can also lead
The acidification of absorbent is caused, and influence of the latter to the pH value of absorbent is more significant, this is because carbon dioxide in methane
Content is far longer than hydrogen sulfide.Absorbent can also reduce absorbent to the absorbability of hydrogen sulfide to the absorption of carbon dioxide.For
It solves the above problems, uses the pH value of sodium carbonate-bicarbonate buffer system control solution in the present invention in absorbent.Natural pond
The gas componant of gas is different from other industrial gasses, and there are the carbon dioxide gas of higher concentration.Due to gas phase dioxy in system
Change carbon-dissolved carbon dioxide-bicarbonate radical-carbonate vapor liquid equilibrium presence, uses sodium carbonate-bicarbonate buffer body
The pH of system's substitution highly basic control system, gaseous pressure caused by can preventing absorbent from absorbing to the hypercapnia in biogas
Decline, while the consumption of lye is substantially reduced, the stabilization of the pH value of absorbent can also be kept, is not appeared in absorption process
The acute variation of pH leads to the decline of assimilation effect.In general, the pH of solution is controlled between 6.0~9.0, it is excessively high to will lead to fortune
Row cost increases and precipitation of iron ions, too low to will lead to assimilation effect decline.Preferably, the pH value of absorbent is in upper range
7.4~8.5, lower range is 6.8~7.2.
Ferric iron in absorbent has strong oxidation as effective component, to the sulphur of negative divalent, by the sulphur of absorption from
Sub- selective oxidation is elemental sulfur, forms precipitating.In the process, ferric iron is reduced to ferrous iron.Ferric iron and ferrous iron
It is easy to happen hydrolysis, hydroxide is formed, is precipitated from aqueous solution, absorbent is caused to fail.In addition to this, due in biogas
The carbon dioxide contained, also will form carbonate deposition.In order to avoid ferro element forms carbonate deposition and hydroxide precipitating,
It needs that complexing ligand is added in absorbent, to form the complex of iron, makes ferric iron and ferrous iron in aqueous solution
Keep solubilised state.Due to ferric iron and the close distribution of ferrous electron cloud and the difference of ionic radius, for the ease of the two
Between conversion, close three complex compound of iron of the stability for needing different ligands to be formed and two complex compound of iron, or have one kind
Play the iron complex of over effect.Alkyl diamine tetraacethyl iron two has preferable stability, three second of ethoxy alkyl diamine
Sour iron three has preferable stability.It is discovered by experiment that the stability of dihydroxy ethyl alkyl diamine oxalic acid iron three is between alkane
Between base ethylenediamine tetraacetic acid (EDTA) iron two and ethoxy alkyl diamine triacetic acid iron three, the over effect of complex compound conversion can be played.
Because oxidation or biochemical degradation will lead to the reduction of the complexing ligand quantity in absorbent, if not sufficient ligand, ferro element meeting
Solution is left in the form of hydroxide or carbonate deposition.In order to avoid above-mentioned phenomenon, the total mole number of complexing ligand is slightly above
The molal quantity of the molal quantity of divalent and ferric iron total amount, complexing ligand and iron is excessive, will lead to material consumption rising, and operating cost increases
Add, preferred complexing ligand total moles are divalent and 1.1 to 1.15 times of molal quantity of ferric iron total amount.Preferably, dihydroxy ethyl
The molar fraction that alkyl diamine oxalic acid accounts for ligand total amount is 0.05~0.1, alkyl diamine tetraacethyl and ethoxy alkyl diamine
The molar ratio range of triacetic acid is 2:1~3:1.
A method of hydrogen sulfide in methane being removed using above-mentioned reproducible absorbent, the equipment used includes that spray is inhaled
Receive tower, sedimentation and regenerating tank, lean pump, discharge pump, oxidation fan, solid-liquid separation unit.This method comprises the following steps: biogas
Enter from the bottom on absorption tower, with the absorption dosage form from the absorbent lean solution counter current contacting under top spraying layer spray, after contact
At rich solution, absorb the bottom of the tower is collected in, sedimentation regenerating tank is flowed automatically to by gravity, the vulcanization in biogas after spray washing
Hydrogen is removed, and leaves purification system by tower top pipeline.
For absorption tower, need to control biogas flow velocity, sprinkle density.The pressure of biogas is lower, typically not greater than 3kpa, this
One advantage of invented technology system is not need to be pressurized biogas, is realized by the following aspects: (1) using lower
Biogas flow velocity, this can reduce the pressure drop in absorption tower, while can prevent absorbent from being carried secretly by biogas, do not need setting remove
Foam device, the pressure drop being further reduced in absorption tower.(2) lesser sprinkle density, the resistance drop in spray absorber are used
Related with spray flow, spray flow influences the key factor of system energy consumption, although spray flow reduction can reduce energy consumption and
Pressure drop, but or else the removal efficiency of hydrogen sulfide can be reduced using in the case where other any special measures.In order to balance above-mentioned ask
Topic, has used N, this hydrogen sulfide stripping synergist of N-dihydroxyalkyl piperazine can promote hydrogen sulfide inhaling in absorbent
The dissolution and acid-base reaction rate in agent are received, to realize the removal efficiency with higher under conditions of low sprinkle density.Together
When, N, N-dihydroxyalkyl piperazine have high fusing point and extremely low vapour pressure, water are highly soluble in, in biogas desulfurization hydrogen
It will not volatilize under environment, compared to general alcohol amine compound, these advantages make N, and N-dihydroxyalkyl piperazine is more suitable and is used for
The hydrogen sulfide stripping technique of biogas.
Contain thinner drusen in rich solution, by absorb the bottom of the tower by gravity, tank level is regenerated by sedimentation
Lower section 1-3 meters of distance enters sedimentation regenerating tank, and by gravitational settling, drusen is settled to tank body lower section.Enter in rich solution
Above mouth tank, air is passed through by oxidation fan, rich solution is regenerated, the rich solution regenerated forms lean solution, is regenerated by sedimentation
To lean solution tank, lean solution tank is used for the interim storage of lean solution for the top outlet overflow of tank, and the lean solution in lean solution tank is pumped by lean pump
Enter absorption tower and spray washing is carried out to biogas.
Drusen absorbent underflow below sedimentation regenerating tank is pumped to solid-liquid separation unit by the discharge pump of bottom, passes through
Separation of solid and liquid is crossed, drusen solid is collected, the liquid after separation of solid and liquid is pumped to the storage of lean solution tank by returning.Sulphur is solid
Body is the byproduct that biogas removes hydrogen sulfide.
For settling regenerating tank, need to control oxidation air flow and discharge pump discharge.Biological desulphurization needs to maintain biology
Activity, therefore setting heating and cooling line control pot temperature, system does not need these affiliated facilities in the present invention,
System energy consumption is lower compared to biological desulphurization.Rich solution is regenerated as lean solution by oxidation air, while excessive oxidation wind can also aoxidize
Complexing ligand causes absorbent to fail, while can also aoxidize part sulphur, so that total salt amount rising easily causes office in system
Portion's crystallization, can also reduce the yield of by-product sulphur.Meanwhile total salt amount rising will lead in absorbent under the percentage composition of water
Drop, so that solvability decline of the hydrogen sulfide from gas phase to liquid phase, causes absorption efficiency to decline, it is therefore desirable to total salt amount
Strict control is carried out, 2.5wt% is usually no more than.In order to avoid the above problem, resist using organic type and the compound of inorganic type
Oxidant: (1) inorganic type is thiosulfate and sulphite, is added at one time when system is driven, in thiosulfate and
In the presence of sulphite is a small amount of in systems, system in the process of running can be spontaneous by simple substance because of being passed through for oxygen
Sulphur is formed, because not needing to supplement in operational process, it is only necessary to is added in first dress.(2) the organic oxidation-resistant agent of polyethers alcohols is added,
On the one hand sulphur can be wrapped up and reduce the contact area of itself and dissolved oxygen to reduce oxidation, on the one hand it can capture oxygen freedom
Base prevents chain type oxidation reaction.Also, polyethers alcohols or a kind of nonionic surface active agent, can reduce the table of absorbent
Face tension, so that the drusen formed in absorbent will not be excessively tiny, convenient for being separated by solid-liquid separation.
Since complex ligands and part of auxiliary are the preferable organic matter of biocompatibility, it is easy by microbial biochemical
Degradation, in the case where especially thering is biogas and oxidation air to enter in systems, it is easier to cause biochemistry caused by microorganism
Degradation.This point is different from other industrial gas purifyings such as natural gas, and biogas derives from anaerobic fermentation, leaves fermentation system entrainment
Droplet in contain a large amount of microorganisms, into these microorganisms in methane purifying system be possible to act on complexing ligand and other
Therefore the biochemical degradation of auxiliary agent in the present invention, joined ionic surfactant into absorbent as biological inhibition
Agent, meanwhile, it can also assist promoting growing up for simple substance sulphur granule.Other than quaternary ammonium salt ionic surfactant,
Other kinds of bacteriostatic agent, such as isothiazolinone, quaternary alkylphosphonium salt, glutaraldehyde etc. can be added.
Following procedure mainly occurs in absorption tower in the present invention:
H2S(g)→H2S(s) (1)
H2S+CO3 2-→HS-+HCO3 - (2)
H2S+HCO3 -→HS-+CO2+H2O (3)
HS-+FeL3+→S+FeL2++H+ (4)
H++CO3 2-→HCO3 - (5)
Following procedure mainly occurs in sedimentation and regenerating tank:
2H2O+O2+4FeL2+→4FeL3++4OH- (6)
OH-+HCO3 -→H2O+CO3 2- (7)
The oxidation of sulphion in the removing and liquid phase of hydrogen sulfide in gas phase occurs in absorption tower, occurs in sedimentation and regenerating tank
The oxidation regeneration of absorbent.
The configuration of 1 absorbent of embodiment and the absorbent properties of hydrogen sulfide
In 5L reactor, successively demineralized water, ferrous sulfate heptahydrate, bodied ferric sulfate, complexing ligand, N, N- dihydroxy is added
It is alkyl piperazine, sodium carbonate and sodium bicarbonate buffer system, nonionic surface active agent, ionic surfactant, anti-oxidant
Agent.15~20min is stirred, the absorbent of clear is obtained, is measured for absorbent properties, the measurement of absorbent properties passes through simulation
The gas-liquid contact of biogas and absorbent.Configuration condition and measurement result are as shown in the table, and hydrogen sulfide stripping efficiency is after running for 24 hours
Testing result.Wherein, that dihydroxy ethyl alkyl diamine oxalic acid, dihydroxy second in sample 1,2,11,12 is not added in sample 10
The molar fraction that base alkyl diamine oxalic acid accounts for complexing ligand is 0.05, dihydroxy ethyl alkyl diamine diethyl in sample 6,7,9,13
The molar fraction that acid accounts for complexing ligand is 0.02, in sample 3 dihydroxy ethyl alkyl diamine oxalic acid account for complexing ligand mole point
Number is 0.08, and it is 0.1 that dihydroxy ethyl alkyl diamine oxalic acid, which accounts for the molar fraction of complexing ligand, in sample 4,8,14,16, sample
It is 0.12 that dihydroxy ethyl alkyl diamine oxalic acid, which accounts for the molar fraction of complexing ligand, in 15.
The configuration of 1 absorbent of table and the absorbent properties tables of data of hydrogen sulfide
2 biogas of embodiment removes hydrogen sulfide demonstration project
Biogas flow 2000m3/ h, 35 DEG C of biogas temperature, biogas pressure 2kPag is passed through tower from bottom by gas distributor
Diameter is 1.4m, is highly 11.5 meters, the spray column containing three layers of spraying layer, and from the absorbent lean solution under top spraying layer spray
Counter current contacting, the absorbent after contact form rich solution, collect in absorb the bottom of the tower, flow automatically to sedimentation regeneration by gravity
Tank, the hydrogen sulfide in biogas after spray washing are removed, and leave purification system by tower top pipeline.The hydrogen sulfide absorbed in rich solution
It is aoxidized to form elemental sulfur by ferric iron, ferric iron back is ferrous iron.After rich solution enters in sedimentation regenerating tank, elemental sulfur is naturally heavy
It is down to tank base, supernatant is contacted with the air that oxidation fan blasts, will be therein ferrous oxidising for ferric iron, oxidation sky
Gas is distributed by gas distributor, and the flow of oxidation air is 260m3/h.The lean solution regenerated is pumped into absorption by lean pump
Tower.The elemental sulfur slurries for being deposited to bottom are pumped into solid-liquid separation unit by discharge pump, after solid-liquid separation unit separates
Elemental sulfur solid phase is collected recycling, and the clear liquid of solid-liquid separation unit settles regenerating tank by reflux pump blowback.Settle regenerating tank
Volume be 38m3.No. 2 in embodiment 1 and No. 16 absorbents are used for the operation of demonstration project, and be added wherein it is non-from
Subtype surfactant, ionic surfactant and antioxidant, operation result are as shown in table 2.Wherein 1~8,13 using suction
Agent 2 are received, 9~12 use absorbent 16.4~5 nonionic surface active agent is not added, and filter effect is remarkably decreased, and 9 are not
Ionic surfactant is added, the increase of desulfuration efficiency at any time continues to decline.When using nonylphenol polyoxyethylene ether, 12
When zephiran, sodium sulfite, polyethylene glycol, the integrated operation performance of system is best.Hydrogen-oxygen is used in 13
Change sodium highly basic and adjust pH, pH not 9.0 when lean solution enters tower, pH value is only 6.7 when leaving absorption tower, and biggish pH fluctuation causes to vulcanize
The absorption efficiency of hydrogen is unstable.
2 biogas of table removes hydrogen sulfide demonstration plant operation data table
Specific case used herein elaborates inventive concept, the explanation of above example is only intended to
Help understands core of the invention thought.It should be pointed out that for those skilled in the art, not departing from this
Under the premise of inventive concept, any obvious modification, equivalent replacement or the other improvements made should be included in the present invention
Protection scope within.
Claims (9)
1. a kind of absorbent for removing hydrogen sulfide in methane, which is characterized in that the absorbent is aqueous solution, and solute includes complexing
Iron and complexing is ferrous, N, N- dihydroxyalkyl piperazine, sodium carbonate and sodium bicarbonate buffer system, nonionic surface active agent, from
Subtype surfactant and antioxidant；Wherein, the concentration of ferro element is 100~2000mg/L, Complexing Iron and complexing ferrous iron
Molar ratio is 0.2~5, controls pH value of solution 6.0~9.0 by sodium carbonate and sodium bicarbonate buffer system, non-ionic surface
The concentration of activating agent is 50~500mg/L, and the concentration of ionic surfactant is 10~100mg/L, N, N- dihydroxy ethyl piperazine
The concentration of piperazine is 10~100mg/L, and the concentration of antioxidant is 50~500mg/L.
2. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the Complexing Iron and complexing
Ferrous complexing ligand is in alkyl diamine tetraacethyl, ethoxy alkyl diamine triacetic acid and dihydroxy ethyl alkyl diamine oxalic acid
One or more.
3. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the N, N- dihydroxyalkyl
Alkyl described in piperazine is ethylidene or propylidene.
4. the absorbent of removing hydrogen sulfide in methane according to claim 3, which is characterized in that the N, N- dihydroxyalkyl
Piperazine is N, one or both of N- dihydroxy ethyl piperazine and N, N- dihydroxypropyl piperazine.
5. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the sodium carbonate-carbonic acid
Hydrogen sodium buffer system includes the one or two of sodium carbonate and sodium bicarbonate.
6. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the non-ionic surface
Activating agent includes one or more of octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, dodecyl polyoxyethylene ether.
7. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the ionic surface is living
Property agent include neopelex, triethyl group lauryl ammonium chloride, tributyl octyl ammonium chloride, tetrabutylammonium bromide and
One or more of dodecyl benzyl dimethyl ammonium chloride.
8. the absorbent of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the antioxidant includes
Polypropylene oxide, hydroquinone, tert-butylhydroquinone, sodium sulfite, sodium thiosulfate, polyethylene glycol and butylated hydroxy-a
One or more of benzene.
9. a kind of method of the removing hydrogen sulfide in methane using any absorbent of claim 1-8, the method make
Equipment includes spray absorber, sedimentation and regenerating tank, lean pump, discharge pump, oxidation fan and solid-liquid separation unit；It is described
Method includes:
The bottom on absorption tower sucks biogas, biogas with from the absorbent lean solution counter current contacting under top spraying layer spray, after contact
Absorbent formed rich solution, collect in absorb the bottom of the tower, sedimentation regenerating tank flowed automatically to by gravity, the natural pond after spray washing
Hydrogen sulfide in gas is removed, and leaves purification system by tower top pipeline.
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