CN110302643A - A kind of device and method removing hydrogen sulfide in methane - Google Patents
A kind of device and method removing hydrogen sulfide in methane Download PDFInfo
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- CN110302643A CN110302643A CN201910693368.3A CN201910693368A CN110302643A CN 110302643 A CN110302643 A CN 110302643A CN 201910693368 A CN201910693368 A CN 201910693368A CN 110302643 A CN110302643 A CN 110302643A
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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
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
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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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/90—Chelants
- B01D2251/902—EDTA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
Abstract
The invention discloses a kind of devices for removing hydrogen sulfide in methane, including absorption tower, sedimentation and regenerating tank, solid-liquid separation unit, absorbent storage tank, buffer solution storage tank and oxidation fan；The absorption tower has biogas import and methane outlet；The sedimentation and regenerating tank include the decanting zone, renewing zone and buffer area being arranged from bottom to top.The present invention also provides methods corresponding with the device, wherein including the absorbent of specific components.The present invention rich carbonated biogas suitable for removing hydrogen sulfide, and under normal temperature and pressure conditions, efficient stable, driving and parking is flexible, debugging cycle is short, energy consumption and material consumption are low, can be used for device load frequently changes.
Description
Technical field
The present invention relates to gas purification technique field, especially a kind of device 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 purpose of the present invention is to provide remove hydrogen sulfide in a kind of carbonated biogas of richness from normal temperature and pressure
Method and apparatus.
To achieve the above object, it in a first aspect, the present invention provides a kind of device for removing hydrogen sulfide in methane, including absorbs
Tower, sedimentation and regenerating tank, solid-liquid separation unit, absorbent storage tank, buffer solution storage tank and oxidation fan；The absorption tower has
Biogas import and methane outlet；
The sedimentation and regenerating tank include the decanting zone, renewing zone and buffer area being arranged from bottom to top；The decanting zone and
Between the renewing zone be equipped with baffle, the baffle and it is described sedimentation and regenerating tank inner wall between there are passing through for liquid between
Gap；
The absorb the bottom of the tower passes through piping connection to the decanting zone, with the rich solution in self-absorption in future tower in decanting zone
Sedimentation, so that supernatant enters renewing zone；The decanting zone is connected to the equipment for separating liquid from solid by discharge pump；
Arrange that oxidation air pipeline and aeration head, the outlet of the oxidation fan are connected to the regeneration in the renewing zone
The supernatant oxidation regeneration is formed lean solution by area；The solid-liquid separation unit is by filtrate pump and piping connection to described
Renewing zone；
The buffer area is equipped with lean solution outlet, and the lean solution for flowing back into the absorption tower again；
The buffer solution storage tank and absorbent storage tank are connected with the buffer area.
Further, for the lean solution outlet by piping connection to lean solution storage tank, the lean solution storage tank passes through lean pump
With piping connection to the absorption tower；Or
The lean solution outlet directly passes through lean pump and piping connection to the absorption tower.
Connection lean solution holding vessel can temporarily store lean solution, and be directly connected to absorption tower and do not need then individually to store lean solution,
It can select to use according to actual needs.
Further, described device further includes pH meter, conductometer and oxidation-reduction potentiometer；The pH meter, conductometer and
The position of oxidation-reduction potentiometer is located at the buffer area to the pipeline between the lean pump.
Further, the biogas import is located at the absorb the bottom of the tower, and absorb the bottom of the tower is equipped with gas distributor, top
Equipped with spraying layer, the quantity of spraying layer is layer 2-4, and the spacing between spraying layer is 0.5~1.5m, the multiple spiral shells of every layer of sparger arrangement
Cyclone nozzle.
Further, the solid-liquid separation unit includes bag filter, vacuum bag filters, centrifuge, sheet frame pressure
Filter and sulphur melt one or more of kettle.
Second aspect, the present invention provide a kind of device removing hydrogen sulfide in methane using above-mentioned removing hydrogen sulfide in methane
Method, include the following steps:
Biogas is sprayed by absorbent, the hydrogen sulfide absorption in biogas is entered into liquid phase and forms rich solution；
In sedimentation and regenerating tank, rich solution is settled, is sent into solid-liquid separation unit and separates, and will be formed after sedimentation
Supernatant oxidation regeneration；The filtrate that solid-liquid separation unit is isolated also enters oxidation regeneration in the sedimentation and regenerating tank；
The lean solution formed by oxidation regeneration is conveyed again, for spraying biogas.
Wherein, the absorbent is aqueous solution, and solute ions include sodium iron ethylene diamine tetra acetate, polyethyleneimine, carbonic acid
Sodium and sodium bicarbonate buffer system, nonionic surface active agent, ionic surfactant, antioxidant；Wherein, ethylenediamine
The concentration of tetraacethyl ferrisodium is 100~2000mg/L, and the concentration of polyethyleneimine is controlled in 10~200mg/L, passes through sodium carbonate
And sodium bicarbonate buffer system control pH value of solution is 6.0~9.0, the concentration of nonionic surface active agent in 50~500mg/L,
The concentration of ionic surfactant is 10~100mg/L, and the concentration of antioxidant is 50~500mg/L.
Further, controlling empty tower gas velocity in absorption tower, within 0.4~1.2m/s, sprinkle density is controlled in 3~12m3/
h/m2。
Further, the pH of the absorbent is controlled 6.0~9.0.
Further, the degree of polymerization of the polyethyleneimine is 10-50.
Further, the sodium carbonate-bicarbonate buffer system includes the one or two of sodium carbonate or sodium bicarbonate；
The nonionic surface active agent includes octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, dodecanol polyoxyethylene
One or more of ether；The ionic surfactant includes neopelex, triethyl group dodecyl chlorination
One or more of ammonium, tributyl octyl ammonium chloride, tetrabutylammonium bromide, dodecyl benzyl dimethyl ammonium chloride；It is described
Antioxidant include polypropylene oxide, hydroquinone, tert-butylhydroquinone, sodium sulfite, sodium thiosulfate, polyethylene glycol,
One or more of dibutyl hydroxy toluene.
Compared with prior art, it is of the invention have the following beneficial effects: that absorbent absorbs hydrogen sulfide after, in sedimentation and again
In raw tank, innovatively it is divided into buffer area, renewing zone and the region of decanting zone three, the design of baffle, makes in sedimentation and regenerating tank
Rich solution and supernatant separation are obtained, can be realized simultaneously two reactions of sedimentation and regeneration, the buffer area of the top can play recycling
The effect of lean solution.Buffering, sedimentation and regeneration can be completed in same tank body, simplify the structure and work of entire reaction system
Skill.In addition, the present disclosure additionally applies for hydrogen sulfide is removed in rich carbonated biogas, under normal temperature and pressure conditions, efficiently steady
Calmly, driving and parking is flexible, debugging cycle is short, energy consumption and material consumption are low, can be used for device load frequently changes.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of device for removing hydrogen sulfide in methane provided in an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of absorption system；
Fig. 3 is the structural schematic diagram of sedimentation and regenerative system；
In figure: 1- spray absorber；2- sedimentation and regenerating tank；3- solid-liquid separation unit；4- absorbent storage tank；5- buffer
Storage tank；6- lean solution supply pump；7- discharge pump；8- filtrate pump；9- oxidation fan；10- absorbent supply pump；11- buffer solution supplies
To pump；101- spraying layer；102- spiral nozzle；The decanting zone 201-；The renewing zone 202-；The buffer area 203-；204- baffle.
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.
The embodiment of the present invention provides a kind of method for removing hydrogen sulfide in methane, using Regeneratable absorbent by absorbing system
System, regenerative system, absorbent feed system and filtration system purify the hydrogen sulfide in biogas:
(1) in absorption system, absorbent carries out spray washing to biogas, and the hydrogen sulfide absorption in biogas is entered liquid phase
And it is oxidized to elemental sulfur, elemental sulfur forms precipitating；
(2) elemental sulfur is precipitated into filtering removal in filtration system；
(3) absorbent after absorbing hydrogen sulfide in regenerative system by oxidation regeneration and is recycled；
(4) due in separation of solid and liquid process solid phase to the absorption of absorbent and other loss, pass through absorbent supply system
System regular replenishment absorbent.
Regeneratable absorbent described in the present embodiment is aqueous solution, and solute ions include sodium iron ethylene diamine tetra acetate (EDTA
Ferrisodium), polyethyleneimine (PEI), sodium carbonate and sodium bicarbonate buffer system, nonionic surface active agent, ionic surface
Activating agent, antioxidant.Wherein, the concentration of NaFeEDTA sodium is in 100~2000mg/L, the concentration control of polyethyleneimine 10~
200mg/L controls pH value of solution 6.0~9.0 by sodium carbonate and sodium bicarbonate buffer system, nonionic surface active agent
Concentration in 50~500mg/L, the concentration of ionic surfactant in 10~100mg/L, the concentration of antioxidant 50~
500mg/L。
Wherein, the degree of polymerization of PEI is 10-50, and the sodium carbonate-bicarbonate buffer system includes sodium carbonate or bicarbonate
The one or two of sodium；The nonionic surface active agent includes octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, ten
One or more of dialkanol polyoxyethylene ether；The ionic surfactant includes neopelex, three second
Base lauryl ammonium chloride, tributyl octyl ammonium chloride, tetrabutylammonium bromide, one in dodecyl benzyl dimethyl ammonium chloride
Kind is several；The antioxidant includes polypropylene oxide, hydroquinone, tert-butylhydroquinone, sodium sulfite, thiosulfuric acid
One or more of sodium, polyethylene glycol, dibutyl hydroxy toluene.
Following procedure mainly occurs for the absorption process 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 for regenerative process:
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.
A kind of device of the method suitable for above-mentioned removing hydrogen sulfide in methane includes spray absorber 1, sedimentation and regeneration
Tank 2, lean solution supply pump 6, discharge pump 7, oxidation fan 9, solid-liquid separation unit 3, filtrate pump 8, absorbent storage tank 4, buffer solution
Storage tank 5, buffer solution supply pump 11, absorbent supply pump 10, pH meter, conductometer, oxidation-reduction potentiometer, device such as Fig. 1 institute
Show:
(1) absorption system includes spray absorber 1 and lean solution supply pump 6；
(2) filtration system includes discharge pump 7, solid-liquid separation unit 3 and filtrate pump 8；
(3) regenerative system includes sedimentation and regenerating tank 2, oxidation fan 9, pH meter, conductometer and oxidation-reduction potentiometer；
(4) absorbent feed system includes absorbent storage tank 4, buffer solution storage tank 5, buffer solution supply pump 11 and inhales
Receive agent supply pump 10.
Wherein, spray absorber 1 is connected with sedimentation and regenerating tank 2 by pipeline, settles and 2 phase of regenerating tank is respectively and solid
Liquid separative unit 3, buffer solution storage tank 5 and absorbent storage tank 4 are connected.1 bottom of spray absorber is equipped with biogas air inlet
And gas distributor (not shown), top are equipped with spraying layer 101, the quantity of spraying layer 101 is layer 2-4, spraying layer 101 it
Between spacing be 0.5~1.5m, every layer of spraying layer 101 arrange multiple spiral nozzles 102, and absorption system structure is as shown in Figure 2.Control
Empty tower gas velocity is within 0.4~1.2m/s in absorption tower processed, it is preferred that empty tower gas velocity is 0.4~0.54m/s.Every layer of spraying layer
101 sprinkle density is controlled in 3~12m3/h/m2, preferred sprinkle density is 6~10m3/h/m2。
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 atmosphere of gas is different from other industrial gasses, and there are the carbon dioxide gas of higher concentration.Due to gas phase titanium dioxide in system
Carbon-dissolved carbon dioxide-bicarbonate radical-carbonate vapor liquid equilibrium presence, uses sodium carbonate-bicarbonate buffer system
The pH for substituting highly basic control system can prevent absorbent from absorbing under caused gaseous pressure to the hypercapnia in biogas
Drop, while the consumption of lye is substantially reduced, the stabilization of the pH value of absorbent can also be kept, pH in absorption process is not appeared in
Acute variation lead 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 operation
Cost increases and precipitation of iron ions, too low to will lead to assimilation effect decline.Preferably, the pH value of absorbent exists in upper range
7.4~8.2, lower range is 6.8~7.2.The NaFeEDTA sodium being added in absorbent has the hydrogen sulfide absorbed in absorbent
Negative divalent sulfur can be oxidized to elemental sulfur by oxidation, while iron ion forms ferrous ion, so that minus two in absorbent
Valence sulphur remains lower concentration in absorption tower so that absorbent and the hydrogen sulfide in gas phase have always it is high opposite
Concentration difference, to realize absorbent to the facilitation of the chemical absorbing of hydrogen sulfide.There are two make for the PEI tool being added in absorbent
With one is using amido abundant in PEI to the cage of the suction-operated of the proton in hydrogen sulfide and the oligomer of macromolecular
Shape shape improves absorbent to the chemical reaction ability of hydrogen sulfide, to promote absorbent to vulcanization to the coating function of hydrogen sulfide
The absorption process of hydrogen；The second is polyamines base has preferable coordination to ferric iron at a high ph in PEI, EDTA can be increased
The solubility of ferrisodium under high ph conditions slows down ferric hydrolytic precipitation reaction, increases the stability of absorbent solution.
Sedimentation and regenerating tank 2 are divided into decanting zone 201, renewing zone 202, the region of buffer area 203 3, renewing zone from bottom to top
Arrangement oxidation air pipeline and aeration head in 202 have the interval of baffle 204 between renewing zone 202 and decanting zone 201, baffle 204
There are certain gaps for the inner wall of edge and tank body, flow into for supernatant, while stopping sediment to turn over and gushing pollution renewing zone 202.
Structure is as shown in Figure 3.The absorbent that spray-absorption tower bottom absorbs hydrogen persulfide forms rich solution, is entered by gravity line
Decanting zone 201, supernatant enter 202 oxidation regeneration of renewing zone, and the supernatant after regeneration enters buffer area 203, precipitate rich in sulphur
Slurries decanting zone 201 settle, formed solid content 1~10vol% underflow.6 entrance of lean solution supply pump is with sedimentation and again
The buffer area 203 of raw tank 2 is connected, and the absorbent after wherein regenerating is pumped into spray absorber 1 and is sprayed, is washed to biogas.
7 entrance of discharge pump is connected with decanting zone 201, by the underflow pump after sedimentation to solid-liquid separation unit 3.Oxidation fan 9 outlet with again
Raw area 202 is connected, and is pumped into air thereto and carries out oxidation regeneration to absorbent clear liquid.PH meter, conductometer and redox electricity
The check bit of position meter is set to buffer area 203 to pipeline (not shown) between lean solution supply pump 6.The setting of above three sensor
In buffer area to the pipeline between lean pump, whether the output quality that lean solution can be monitored in real time is up to standard, if not up to standard not
It opens lean pump or stops lean pump immediately, lean solution not up to standard is avoided to flow into absorption tower.
Contain thinner drusen in rich solution, by absorb the bottom of the tower by gravity, by liquid level in sedimentation regenerating tank 2
Lower section 1-3 meters of distance enters sedimentation regenerating tank 2, 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 9, rich solution is regenerated, the rich solution regenerated forms lean solution, by sedimentation and again
The top outlet overflow of raw tank 2 connects spray absorber 1 to lean solution tank or directly by lean solution supply pump.If using lean solution
Tank, then lean solution tank can be used for the interim storage of lean solution, and the lean solution in lean solution tank is pumped into absorption tower by lean pump and carries out to biogas
Spray washing.
The drusen absorbent underflow of 2 lower section of sedimentation and regenerating tank is pumped to separation of solid and liquid list by the discharge pump 7 of bottom
Member 3 collects drusen solid by being separated by solid-liquid separation, and the liquid after separation of solid and liquid, which returns, is pumped to the slow of sedimentation and regenerating tank 2
Rush area 203.Sulphur solid is the byproduct that biogas removes hydrogen sulfide.
For sedimentation and regenerating tank, need to control oxidation air flow and discharge pump discharge.Biological desulphurization needs to maintain life
Object activity, therefore heating is arranged and cooling line controls pot temperature, system does not need these and attached sets in the present invention
It applies, system energy consumption is lower compared to biological desulphurization.Rich solution is regenerated as lean solution by oxidation air, while excessive oxidation wind also can oxygen
Change complexing ligand, cause absorbent to fail, while can also aoxidize part sulphur, so that total salt amount rising easily causes in system
It is local-crystalized, it 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.
Filter plant can use bag filter, vacuum bag filters, centrifuge, plate compression in solid-liquid separation unit
Machine and sulphur melt one or more of kettle.Filtrate pump intake is connected with solid-liquid separation unit, the clear liquid after being separated by solid-liquid separation
It is pumped into sedimentation and regenerating tank renewing zone bottom by filtrate pump, filtered elemental sulfur solid phase discharge system forms solid content and exists
The byproduct of 50~99vol%.
The amount of storage of absorbent can satisfy system 14~20 days or so absorbent magnitude of recruitments, delay in absorbent storage tank 4
The amount of storage for rushing buffer solution in solution reservoir 5 can satisfy system 18~24 days or so buffer solution magnitude of recruitments.Absorbent
10 entrance of supply pump is connected with absorbent storage tank 4, exports and settles and 2 buffer area of regenerating tank, 203 bottom is connected.It buffers molten
11 entrance of fluid supply pump is connected with buffer solution storage tank 5, exports and settles and 2 buffer area of regenerating tank, 203 bottom is connected.
Biogas enters from the bottom of spray absorber 1, connects with from the absorbent lean solution adverse current under the spray of top spraying layer 101
Touching, the absorbent after contact form rich solution, collect in 1 bottom of spray absorber, flow automatically to sedimentation and regeneration by gravity
Tank 2, the hydrogen sulfide in biogas after spray washing are removed, and leave purification system by tower top pipeline.Due to the gas of coming of biogas
Pressure is lower, typically not greater than 3KPa.The pressure drop of the gas-liquid mass transfer (contact) equipments such as packed tower, bubble tower is larger, is not having to supercharging equipment
In the case where, marsh gas purifying technique is suitble to using spray column, and this point is different from other industrial gas purifyings such as natural gas.If
Biogas is pressurized using supercharging equipment, it can also be using gas-liquid mass transfer (contact) equipments such as packed tower, bubble towers.For spray-absorption
Tower needs to control biogas flow velocity, sprinkle density, spray layer number and spacing.
One advantage of present invention process system is not need to be pressurized biogas, is realized by the following aspects:
(1) lower biogas flow velocity is used, this can reduce the pressure drop in absorption tower, while can prevent absorbent from being carried secretly by biogas,
Setting Despumation device, the pressure drop being further reduced in absorption tower are not needed.(2) lesser sprinkle density, spray-absorption are used
Resistance drop in tower is related with spray flow, and spray flow influences the key factor of system energy consumption, although reduce can be with for spray flow
Energy consumption and pressure drop are reduced, but or else can reduce the removal efficiency of hydrogen sulfide using in the case where other any special measures.For
The balance above problem, this hydrogen sulfide stripping synergist of PEI has been used in absorbent, hydrogen sulfide can be promoted to absorb
Dissolution and acid-base reaction rate in agent, to realize the removal efficiency with higher under conditions of low sprinkle density.Meanwhile
Meanwhile used PEI is organic macromolecule oligomerization compounds, has extremely low vapour pressure and is highly soluble in water, in natural pond
It will not volatilize in the environment of qi exhaustion hydrogen sulfide, compared to general alcohol amine compound, these advantages make PEI be more suitable for natural pond
The hydrogen sulfide stripping technique of gas.
Present invention process system another advantage is that have good biological oxidation stability, especially suitable for biomass
The purification of energy gas: it since complex ligands and part of auxiliary are the preferable organic matter of biocompatibility, is easy micro-
Biological biochemistry degradation, in the case where especially thering is biogas and oxidation air to enter in systems, it is easier to microorganism be caused to be led
The biochemical degradation of cause.This point is different from other industrial gas purifyings such as natural gas, and biogas derives from anaerobic fermentation, leaves fermentation
Contain a large amount of microorganisms in the droplet of system entrainment, is possible to act on NaFeEDTA into these microorganisms in methane purifying system
It receives and therefore the biochemical degradation of other auxiliary agents in the present invention, joined ionic surfactant into absorbent as life
Object inhibitor, meanwhile, it can also assist promoting growing up for simple substance sulphur granule.In addition to quaternary ammonium salt ionic surfactant with
Outside, other kinds of bacteriostatic agent, such as isothiazolinone, season squama salt, glutaraldehyde etc. can also be added.
In conclusion technical advantage of the invention: (1) suitable for removing hydrogen sulfide rich carbonated biogas；
(2) unique absorbent formula designs so that absorbent is easy the hydrogen sulfide absorption in gas phase entering liquid phase simultaneously in use
The sulphur of negative divalent is efficiently oxidized to elemental sulfur, is used so that absorbent to organo-mineral complexing antioxidant and bacteriostatic agent
With long-time stability；(3) with the matching used hydrogen sulphide removal unit of absorbent and method, especially suitable for wider hydrogen sulfide
The marsh gas purifying of concentration range, low gas phase temperature and pressure.
The present invention be it is a kind of have under normal temperature and pressure conditions, efficient stable, driving and parking is flexible, debugging cycle is short, energy consumption and
The method and device for the removing hydrogen sulfide in methane that material consumption is low, can be used for device load frequently changes.
The configuration of 1 absorbent of application examples and the absorbent properties of hydrogen sulfide
The present invention is further illustrated according to specific embodiment.
In 5L reactor, successively demineralized water, NaFeEDTA sodium, PEI, sodium carbonate and sodium bicarbonate buffer system, non-is added
Ionic surfactant, ionic surfactant, antioxidant.15~20min is stirred, the absorption of clear is obtained
Agent is measured for absorbent properties, the gas-liquid contact that the measurement of absorbent properties passes through simulation biogas and absorbent.Configuration condition and survey
Determine that result is as shown in the table, hydrogen sulfide stripping efficiency is the testing result after operation for 24 hours.Wherein, it is not added in sample 1 and 6
PEI, NaFeEDTA sodium is dissolved completely in aqueous solution in acid condition, is adjusting pH value to weak basic condition using buffering dissolution
Afterwards, there is partial suspended thing precipitation in solution.The effect that suspended state absorbs hydrogen sulfide to absorbent plays the role of decrease.
The configuration of 1 absorbent of table and the absorbent properties tables of data of hydrogen sulfide
2 biogas of application examples removes hydrogen sulfide demonstration project
Biogas flow 2000m3/ h, 35 DEG C of biogas temperature, biogas pressure 2KPag is passed through by gas distributor from bottom
Tower diameter is 1.4m, is highly 11.5 meters, the spray column containing three layers of spraying layer, and poor from the absorbent under top spraying layer spray
Liquid 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 250m3/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.Wherein, liquid-gas ratio control is absorbed in 0.03~0.08m3/m3, regeneration gas liquid ratio control is in 2.1~2.6m3/
m3.No. 2 in application examples 1 and No. 8 absorbents are used for the operation of demonstration project, and non-ionic surfactant is added wherein
Agent, ionic surfactant and antioxidant, operation result are as shown in table 2.Wherein 1~8,13 use absorbent 2,9~
12 use absorbent 8.4~5 nonionic surface active agent is not added, and filter effect is remarkably decreased, and 9 ionic table is not added
Face activating agent, the increase of desulfuration efficiency at any time continue to decline.When using nonylphenol polyoxyethylene ether, dodecyl dimethyl benzyl
When ammonium chloride, sodium sulfite, polyethylene glycol, the integrated operation performance of system is best.It is adjusted in 13 using sodium hydroxide highly basic
PH, pH is 9.0 when lean solution enters tower, and pH value is only 6.7 when leaving absorption tower, and biggish pH fluctuation leads to the absorption efficiency of hydrogen sulfide
It is unstable.
2 biogas of table removes hydrogen sulfide demonstration plant operation data table
The vulcanisation hydrogen engineering of 3 kitchen biogas qi exhaustion of application examples
The fermentation of certain food wastes generates biogas 700Nm3/ h, 35 DEG C of biogas temperature, biogas pressure 2KPag, wherein sulphur
Change hydrogen content 5000ppm, the target content of hydrogen sulfide in methane reaches 100ppm or less after hydrogen sulfide stripping engineering.Removing
Engineering uses vulcanization hydrogen purification process of the present invention, using absorbent 2.Being passed through tower diameter from bottom by gas distributor is
1.0m, be highly 10.5 meters, the spray column containing three layers of spraying layer, with from the lower absorbent lean solution of top spraying layer spray countercurrently
Contact, the absorbent after contact form rich solution, collect in absorb the bottom of the tower, flow automatically to sedimentation regenerating tank by gravity, spray
The hydrogen sulfide eluted in the biogas after washing is removed, and leaves purification system by tower top pipeline.The hydrogen sulfide absorbed in rich solution is by three
Valence iron aoxidizes to form elemental sulfur, and ferric iron back is ferrous iron.After rich solution enters in sedimentation regenerating tank, elemental sulfur natural subsidence is extremely
Tank base, supernatant are contacted with the air that oxidation fan blasts, by it is therein it is ferrous oxidising be ferric iron, oxidation air is logical
Gas distributor distribution is crossed, the flow of oxidation air is 140m3/h.The lean solution regenerated is pumped into absorption tower by lean pump.It is heavy
The elemental sulfur slurries for dropping to bottom are pumped into solid-liquid separation unit by discharge pump, the elemental sulfur after solid-liquid separation unit separates
Solid phase is collected recycling, and the clear liquid of solid-liquid separation unit settles regenerating tank by reflux pump blowback.Settle the volume of regenerating tank
For 13m3.Using conduct when nonylphenol polyoxyethylene ether, dodecyl benzyl dimethyl ammonium chloride, sodium sulfite, polyethylene glycol
Absorb agent aid.During system is run 2 months, the concentration of hydrogen sulfide in biogas after hydrogen sulfide stripping engineering is protected always
Hold 10~15ppm.
4 feces of farm biogas of application examples removes hydrogen sulfide engineering
The fermentation of certain planningization feces of farm generates biogas 833Nm3/ h, 33 DEG C of biogas temperature, biogas pressure 3KPag,
Middle hydrogen sulfide content 8000ppm, the target content of hydrogen sulfide in methane reaches 50ppm or less after hydrogen sulfide stripping engineering.
It removes engineering and uses vulcanization hydrogen purification process of the present invention, be passed through tower from bottom by gas distributor using absorbent 3
Diameter is 1.0m, is highly 12.0 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 160m3/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 16m3.Using nonylphenol polyoxyethylene ether, dodecyl benzyl dimethyl ammonium chloride, sodium sulfite, polyethylene glycol
Shi Zuowei absorbs agent aid.During system is run 6 months, the concentration of hydrogen sulfide in biogas after hydrogen sulfide stripping engineering
It is always maintained at 10~20ppm
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 (10)
1. a kind of device for removing hydrogen sulfide in methane, which is characterized in that including absorption tower, sedimentation and regenerating tank, separation of solid and liquid
Unit, absorbent storage tank, buffer solution storage tank and oxidation fan；The absorption tower has biogas import and methane outlet；
The sedimentation and regenerating tank include the decanting zone, renewing zone and buffer area being arranged from bottom to top；The decanting zone and described
Baffle is equipped between renewing zone, there are the gaps passed through for liquid between the baffle and the sedimentation and the inner wall of regenerating tank；
The absorb the bottom of the tower is heavy in decanting zone with the rich solution in self-absorption in future tower by piping connection to the decanting zone
Drop, so that supernatant enters renewing zone；The decanting zone is connected to the equipment for separating liquid from solid by discharge pump；
Arrange that oxidation air pipeline and aeration head, the outlet of the oxidation fan are connected to the renewing zone in the renewing zone,
To form lean solution for the supernatant oxidation regeneration；The solid-liquid separation unit by filtrate pump and piping connection to it is described again
Raw area；
The buffer area is equipped with lean solution outlet, and the lean solution for flowing back into the absorption tower again；
The buffer solution storage tank and absorbent storage tank are connected with the buffer area.
2. the device of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the lean solution outlet passes through
For piping connection to lean solution storage tank, the lean solution storage tank passes through lean pump and piping connection to the absorption tower；Or
The lean solution outlet directly passes through lean pump and piping connection to the absorption tower.
3. the device of removing hydrogen sulfide in methane according to claim 2, which is characterized in that described device further includes pH
Meter, conductometer and oxidation-reduction potentiometer；The position of the pH meter, conductometer and oxidation-reduction potentiometer is located at the buffer area
Pipeline between to the lean pump.
4. the device of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the biogas import is located at institute
Absorb the bottom of the tower is stated, absorb the bottom of the tower is equipped with gas distributor, and top is equipped with spraying layer, and the quantity of spraying layer is layer 2-4, spray
Spacing between layer is 0.5~1.5m, the multiple spiral nozzles of every layer of sparger arrangement.
5. the device of removing hydrogen sulfide in methane according to claim 1, which is characterized in that the solid-liquid separation unit packet
It includes bag filter, vacuum bag filters, centrifuge, plate and frame filter press and sulphur and melts one or more of kettle.
6. a kind of method using the device removing hydrogen sulfide in methane for removing hydrogen sulfide in methane described in claim 1, special
Sign is, includes the following steps:
Biogas is sprayed by absorbent, the hydrogen sulfide absorption in biogas is entered into liquid phase and forms rich solution；
In sedimentation and regenerating tank, rich solution is settled, is sent into solid-liquid separation unit and separates, and is upper by what is formed after sedimentation
Clear liquid oxidation regeneration；The filtrate that solid-liquid separation unit is isolated also enters oxidation regeneration in the sedimentation and regenerating tank；
The lean solution formed by oxidation regeneration is conveyed again, for spraying biogas；
Wherein, the absorbent be aqueous solution, solute ions include sodium iron ethylene diamine tetra acetate, polyethyleneimine, sodium carbonate and
Sodium bicarbonate buffer system, nonionic surface active agent, ionic surfactant, antioxidant；Wherein, ethylenediamine tetrem
The concentration of sour ferrisodium is 100~2000mg/L, and the concentration of polyethyleneimine is controlled in 10~200mg/L, passes through sodium carbonate and carbon
Sour hydrogen sodium buffer system control pH value of solution is 6.0~9.0, and the concentration of nonionic surface active agent is in 50~500mg/L, ion
The concentration of type surfactant is 10~100mg/L, and the concentration of antioxidant is 50~500mg/L.
7. according to the method described in claim 6, it is characterized in that, control absorption tower in empty tower gas velocity 0.4~1.2m/s with
Interior, sprinkle density is controlled in 3~12m3/h/m2。
8. according to the method described in claim 6, it is characterized in that, the pH of the absorbent is controlled 6.0~9.0.
9. according to the method described in claim 6, it is characterized in that, the degree of polymerization of the polyethyleneimine is 10-50.
10. according to the method described in claim 6, it is characterized in that, the sodium carbonate-bicarbonate buffer system includes carbonic acid
The one or two of sodium or sodium bicarbonate；The nonionic surface active agent is poly- comprising octyl phenol polyoxyethylene ether, nonyl phenol
One or more of ethylene oxide ether, dodecanol polyoxyethylene ether；The ionic surfactant includes detergent alkylate
Sodium sulfonate, triethyl group lauryl ammonium chloride, tributyl octyl ammonium chloride, tetrabutylammonium bromide, dodecyl dimethyl benzyl
One or more of ammonium chloride；The antioxidant includes polypropylene oxide, hydroquinone, tert-butylhydroquinone, sulfurous
One or more of sour sodium, sodium thiosulfate, polyethylene glycol, dibutyl hydroxy toluene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114367169A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Flue gas renewable desulfurization device and method |
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