CN103254957B - Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) - Google Patents
Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) Download PDFInfo
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Abstract
The invention provides a device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III). According to the device and the method, collagenous fiber/polyester is taken as a carrier to absorb and load Fe(III); when methane passes through an absorption tower which is full of the collagenous fiber/polyester composite material loaded with Fe(III), H2S in the methane is oxidized into elemental sulfur by Fe(III); and Fe(III) is converted into Fe(II). Under the washing action of a circulation liquid, the elemental sulfur and Fe(II) are washed out from the absorption tower, the elemental sulfur is separated through sedimentation and filtration; when the circulation liquid containing Fe(II) passes through an oxidization tower, Fe(II) is oxidized into Fe(III) by air and reenters the absorption tower through the circulation liquid, so as to remove H2S out of the methane. According to the method, the Fe(III) as a desulfurizing agent can be regenerated, H2S in the methane can be removed to be less than 0.5ppm.
Description
Technical field
The invention belongs to biological renewable energy field, particularly one is utilized collegen filament/polyester composite load Fe(III) remove the device and method of hydrogen sulfide in methane.
Background technology
Natural biogas is a kind of low heating value gas, and use range is extremely limited, and efficiency is low, and some national existing biogas industry mainly make its heat production or generating by Gas application in cooking stove and the engine of improvement, as the energy for local user.The relative content that can improve methane in its composition after biogas is purified, increases its calorific value, and the biogas after purifying is mainly for pipe network energy supply or as fuel for motor vehicle as a kind of novel energy at present abroad.The main process of biogas purifying comprises: remove hydrogen sulfide, carbonic acid gas and water and other not combustion-supporting impurity.Wherein, H
2s is always present in biogas, although its content is because the difference of fermentation raw material changes to some extent, must be removed, in order to avoid corrosion compressor, gas storage tank and engine.As biogas contains a certain amount of hydrogen sulfide, also containing the organosulfur of minute quantity, hydrogen sulfide is hypertoxic objectionable impurities sometimes, in air, can make people fatal containing in 0.1% hydrogen sulfide several seconds.It has very deep-etching effect to pneumatic tube, instrument, combustion equipment, and its products of combustion sulfurous gas is also the gas that a kind of corrodibility is very strong, enters atmosphere simultaneously and can produce " acid rain ".For ensureing HUMAN HEALTH and environment protection, in the work-ing life of prolongation gas-fired equipment etc., must in marsh gas purifying process, be carried out as early as possible desulfurization.
For removing of hydrogen sulfide in methane, major technique is as follows:
1, dry desulfurization
Dry desulfurization is usually used in the processing of lean sulphurous gas, and common method has activated carbon method, membrane separation process, pressure-variable adsorption (PSA) method and non-renewable ADSORPTION IN A FIXED BED method etc.Biogas desulfurization is commonly used non-renewable ADSORPTION IN A FIXED BED method, and its method has a lot, is broadly divided into iron system, zinc system, gac etc. from system, is usually used in the de-process of essence of lean sulphurous gas.
At present, state's inner desulfurization technology comparative maturity, sulfur method and sulfur removal technology are numerous, but all exist following shortcoming: dry desulfurization efficiency is not high, desulfurizer regeneration difficulty, Sulfur capacity is relatively low, operate discontinuous, change the shortcomings such as the large and plant area area of sweetening agent labour intensity is large, be mainly applicable to meticulous desulfurization.
1) activated carbon method
The advantage that gac is had compared with other sorbent materials (as molecular sieve) is flourishing specific surface, microvoid structure, thermostability, can optionally remove some chemistry in liquid phase or gas phase, high loading capacity and cheap etc. in moisture.It has acceleration H at normal temperatures
2s is oxidized to the katalysis of sulphur and makes it to be adsorbed.Be adsorbed on the sulphur on gac, the free sulphur on the ammonium sulfide solution extraction gac that available quality mark is 12%-14% is recycled.
Activated carbon method is applicable to H
2s content is less than the desulfurization requirement of 0.3% biogas, therefore can consider to purify with activated carbon method the biogas of big-and-middle-sized biogas engineering.Have the depriving hydrogen sulphide experimental study of closing in Sweet natural gas and show, its desulfurization degree can reach more than 99%, the H of gas after purifying
2s content is less than 10 × 10
-6g/m
3.Its advantage is that simple operation just can obtain the sulphur of high purity, if select suitable gac, can also remove organic sulfide.H
2s and fast (the charcoal absorption H of reacting of gac
2the speed of S is faster than ironic hydroxide), duration of contact is short, it is large-minded to process.
As adopt double bed activated carbon system, also have the following advantages: when two adsorption bed tandem workings, at first adsorption bed absorption H
2another adsorption bed inoperative when S.When first adsorption bed adsorbs when saturated, H
2s can be adsorbed through entering second adsorption bed.As the H of first adsorption bed outflow
2the content of S equals the H in air inlet
2when S content, change the gac of first adsorption bed.After replacing, new adsorption bed is as second active-carbon bed working on.This mode of operation can maximally utilise gac and adsorb.
2) membrane separation process
20 century 70s start, and many countries have carried out commerical test to membrane separation technique for gas delivery in the world.The method is convenient, flexible, can adapt to various operational conditions and change, and processing costs is relatively low, and therefore, membrane separation process is for separating of a large amount of H
2s and CO
2, there are very large potentiality, and little to environmental influence.Although membrane separation process has its inherent advantage, so far not yet in industrial widespread use, major cause is that complicated filming technology makes film system cost costliness.Under this external industrial condition, the performance of separatory membrane is also stable not.
3) ferric oxide absorption process
Ferric oxide absorption process is by Fe
2o
3bits (or powder) and wood chip are mixed and made into sweetening agent, are filled in desulfurizer with hygrometric state (moisture 40% left and right).Fe
2o
3sweetening agent is strip vesicular structure solid, to H
2s can carry out irreversible chemical absorption fast, can be by H in the several seconds
2s is removed to below 1ppm.
While adopting iron oxide process desulfurization, the hydrogen sulfide in biogas carries out chemical reaction on the surface of solid oxidation iron, and the flow velocity of biogas in devulcanizer is less, and duration of contact is longer, and reaction is carried out more fully, and sweetening effectiveness is also just better.After sweetening agent work certain hour, its active can decline gradually, sweetening effectiveness is variation gradually.Generally, as H in desulfurizer outlet biogas
2the content of S exceedes 20mgm
-3time, just need to process sweetening agent; In the time that in sweetening agent, sulphur does not reach 30%, sweetening agent can be regenerated, and deactivated sweetening agent is contacted with air, and iron sulphide oxidation is separated out to sulphur, can make the desulfurizer regeneration losing efficacy; When the iron sulphide massfraction in sweetening agent reaches 30% when above, the obvious variation of sweetening effectiveness, sweetening agent can not continue to use, and will more renew sweetening agent.
The advantage of iron oxide process is Fe
3+there is quite high redox potential, can be by S
2-be converted into elemental sulfur, elemental sulfur can not be further oxidized to vitriol again; The simple substance sulphur granule generating in the absorption process of hydrogen sulfide has katalysis to whole absorption process; In addition ferric oxide aboundresources, cheap and easy to get, is maximum biogas desulfurization method that uses at present.But the absorption that its shortcoming is sweetening agent need hocket with regeneration, thereby has increased labour intensity, affect the continuity of equipment operation.
4) zinc oxide absorption process
Use above-mentioned ferric oxide desulfurizer instead zinc oxide as sweetening agent, just formed the zinc oxide method biogas desulfurization method of purification.Zinc oxide also has the function that Partial Conversion absorbs, can be by CO
2, CS
2become hydrogen sulfide and absorbing and removing Deng organosulfur Partial Conversion.Due to the difficult dissociation of the ZnS generating, and desulfurization precision is high, and the gas sulphur content after desulfurization is 0.1 × 10
-6mg/m
3below.So be applied to smart sweetening process always.Zinc oxide method biogas desulfurization purification techniques is compared with iron oxide process, and its desulfuration efficiency is high, absorption H
2the speed of S is fast.Zinc oxide desulfurization ability increases with temperature, but removes H
2s at a lower temperature (200 DEG C) can carry out, thereby has saved energy consumption cost.The method is suitable for processing H
2the gas that S concentration is lower, desulfuration efficiency is high, and the experimental study according to it in industrial gas desulfurizing and purifying shows, and its desulfurization degree can reach 99%.
But after zinc oxide desulfurization, generally can not reply sweetening power by simple way, and at present zinc oxide Sulfur capacity is low at normal temperatures, and expensive.
5) ferrimanganic zinc composite oxide absorption process
Ferrimanganic zinc composite oxide is a kind of new catalyst, can claim MF.1 type sweetening agent, for the desulfurization of raw material of Large Scale Synthetic Ammonia Plants and Methanol Plant.This catalyzer, taking oxide compounds such as iron content, manganese, zinc as main active component, adds the machine-shapings such as a small amount of promotor and lubricant.
The advantage of ferrimanganic zinc composite oxide doctor treatment is as follows: desulfurization cost saving, and its process cost is all economized than general certain methods; Effective, desulfurization precision height can be by total desulfurization to 0.5 × 10 in Sweet natural gas
-6below; 3, equipment is simple, stable, and turndown ratio is large; Pressure Drop is little, even if the stagnation pressure of entrance Sweet natural gas is low to moderate 1kg/cm
2(gauge pressure), also unlikely cause the underproduction stop; Desulfurization principle is thermal chemical reaction, and in sweetening process, the active ingredient reaction in gas generates stably metallic sulfide, to environment non-secondary pollution.
The shortcoming of iron, manganese, zinc mixed oxide doctor treatment is that desulfurization needs heating installation.Study from reaction mechanism, iron, manganese, zinc mixed oxide doctor treatment also can be applicable to the desulfurizing and purifying of big-and-middle-sized biogas, but concrete technique, data still need further further investigation.
2, wet desulphurization
Wet desulphurization has direct oxidation method, chemical absorption method, chemical oxidization method, physical absorption method.At present domestic conventional be mainly direct oxidation method desulfurization, hydrogen sulfide is oxidized in liquid phase to elemental sulfur, flow process is fairly simple, can directly obtain elemental sulfur.This method is large mainly for the treatment of amount, concentration of hydrogen sulfide is compared with gas low and that gas concentration lwevel is higher.The treatment soln internal circulating load of wet desulphurization treatment capacity large, that reclaim sulphur is large, desulfuration efficiency is high, can operate continuously, be applicable to the gas of desulfurization amount <10t/d.But investment working cost is also high, and biogas utilization general user is difficult to bear.
Wherein chemical oxidization method is, by oxygenant, sulfide is converted into elemental sulfur.If adopt the redox potential of oxygenant too high, in product, elemental sulfur can further be converted into vitriol, makes desulfurization not thorough, thereby affects the efficiency of desulfurization.
1) sodium carbonate absorption process
Present method adopts sodium carbonate solution to absorb sour gas, and due to weakly acidic shock absorption, pH can not change very soon, has ensured the operational stability of system.In addition, sodium carbonate solution absorbs H
2s is than absorbing CO
2hurry up, because these two kinds of sour gas in biogas exist simultaneously, can partly select to absorb H
2s.This method is generally used for removing a large amount of CO from gas
2, also can be used for removing containing CO
2with the sour gas in Sweet natural gas and the biogas of hydrogen sulfide, in purified gas, hydrogen sulfide mass concentration drops to 20mg/m
3.
The major advantage of the method is that equipment is simple, economical.Main drawback is that a part of sodium carbonate has become Sodium Hydrogen Carbonate and assimilated efficiency is reduced, and a part becomes vitriol and is consumed, thereby needs to supplement in time sodium carbonate, thereby increases human cost; In actual motion, the absorption of sodium carbonate solution is subject to the impact of the factors such as flow velocity, flow, temperature, H
2the solubleness of S does not probably reach 100%; In addition, easily form NaHS but not Na when desulfurization
2s, meeting and O when NaHS regeneration
2reacting generating salt and thiosulphate, objectionable impurities is enrichment in absorption liquid, and the receptivity of solution is reduced, thereby needs irregular eliminating desulphurization circulating liquid, has wasted a large amount of raw and auxiliary materials and also may bring secondary environmental pollution.
2) ammonia absorption method
Adopt the hydrogen sulfide in alkaline ammonia absorption biogas, the first stage is physical dissolution process, and in gas, hydrogen sulfide is dissolved in ammoniacal liquor; Subordinate phase is MODEL OF CHEMICAL ABSORPTION PROCESS, and hydrogen sulfide and the ammonium hydroxide of dissolving play neutralization reaction.Renovation process is toward being blown into air containing in the solution of ammonium hydro sulfide, to produce the inverse process of absorption reaction, hydrogen sulfide being parsed.Solution of ammonium hydroxide after parsing, after supplementing fresh ammoniacal liquor, continues on for absorbing; The hydrogen sulfide producing when regeneration must carry out secondary processing, avoids causing environmental pollution.As adopt the desulfurization of ammoniacal liquor liquid-phase catalysis, and by the oxygenizement of solution Resorcinol, make Oxidation of Hydrogen Sulfide become elementary sulfur and separated, solution obtains regeneration simultaneously.
The shortcoming of the method be the sulfur granules that generates due to thinner, be difficult for filtered and recycled, to filler and wall strong adhesion, Ta Neiyi forms the stifled impact of sulphur and produces, ammonia process adopts ammoniacal liquor to make absorption agent in addition, larger to equipment corrosion, and contaminate environment.
3) naphthoquinones oxidation-air regenesis method doctor treatment
There are some researches show, some quinone is that thing has the ability that hydrogen sulfide is converted into elemental sulfur, because they have suitable redox potential, but due to special separately physical properties and chemical property, not all quinone is the application that thing is all suitable for engineering.In addition, contain the carbonic acid gas that concentration is higher in biogas, the generation of side reaction also makes the application of these materials be subject to restriction to a certain degree.Naphthoquinones is a kind of material in thing as quinone, has sufficiently high redox potential, water-soluble, under normal temperature, does not distil, non-volatile, and in the process as oxygenant oxidation of sulfureted hydrogen, is not subject to the impact of carbonic acid gas.
Naphthoquinones desulfuration efficiency is very high and be not subject to the impact of temperature, just can approach 100% and complete under normal temperature condition.In addition, the method is also applicable to the conversion process of gaseous hydrogen sulfide to elemental sulfur, therefore can be widely used in chemical plant, the sweetening process of the anaerobic treatment facility of refinery and sewage.But while adopting naphthoquinones desulfurization, should be noted the loss that has part naphthoquinones along with the separation of elemental sulfur, for the balance that maintains absorption agent need to constantly be supplemented absorption agent in system, because the price comparison of naphthoquinones is expensive, so the desulfurization of naphthoquinones method is not used widely.
4) HPAS oxidation-air regenesis method doctor treatment
HPAS oxidation-air regenesis method is with Na
3pMo
12o
40and NaCl, Na
2cO
3, and NaNO
3the mixture solution of composition is sorbent material, at normal temperatures hydrogen sulfide is converted into elemental sulfur.After flocculation, gravity separation, obtain sulphur mud.Under the effect of reduction-state HPAS oxygen in air, be converted into oxidation state HPAS and recycle.
In the method, HPAS has suitable redox potential, makes it just hydrogen sulfide to be converted into elemental sulfur, and self can regenerate by ingress of air again.In order to improve assimilated efficiency and the regeneration efficiency of absorption agent, need to add a small amount of sodium carbonate and sodium-chlor.In addition, absorption process and regenerative process temperature influence hardly, can complete under normal temperature.Not enough is the problem that the method exists absorption agent to run off equally, needs constantly to supplement absorption agent to ensure the normal operation of system.So far, the method is also in relevant conceptual phase, there is no the report of practical application.
5) Zn/Fe system wet method catalytic oxidation
The method adopts containing the mixing solutions of Zn and Fe and makes sweetening agent, reacts with the S dissolving in solution by Zn, and the form precipitating with the ZnS of low solubility product realizes H
2s efficiently removes; Then ZnS is oxidized to highly purified elementary sulfur by the Fe in solution, and discharge Zn circulation desulfurization; Regularly oxidation regeneration active ingredient Fe manually separates elementary sulfur simultaneously, and desulfurization system reduces completely, recycles.Whole process is equivalent to liquid-phase catalysis reaction H
2s=S+H
2, the hydrogen sulfide that enters as seen devulcanizer is finally removed with the form of sulphur and hydrogen, in reactor, does not accumulate, thereby has advantages of that desulfurization capacity is large.
Whole process does not consume any industrial chemicals, and active ingredient is without degraded.Its main excellent feature is as follows: 1, H in Zn/Fe system wet method catalytic oxidative desulfurization biogas
2the novel method of S, under the operation conditions optimization in laboratory, desulfuration efficiency reaches more than 99.6%; 2, this system desulfurization is subject to the impact of initial pH and gas-liquid contact time larger; 3, can absorb-recycling utilization of doctor solution, product sulphur is easily separated, and desulfurization capacity is large, and regeneration is convenient, and running cost is low; 4, technique, equipment are simple, and turndown ratio is large, and reagent is cheap and easy to get, and process does not consume any industrial chemicals except consuming electric energy, can not produce secondary pollution, and system is without degradation problem.
6) iron trichloride absorption-electrochemical regeneration doctor treatment
Due to Fe
3+have unique chemical property with and in the unique features of sweetening process, utilize iron trichloride as extremely researchist's the concern of absorption agent desulfurization technology.Adopt in recent years electrolysis electrochemical to absorb electrochemical regeneration desulfurization technology to iron trichloride and brought new impact.Iron trichloride absorption-electrochemical regeneration method sweetening process is as follows:
Absorption process: H
2s (g)---H
2s (aq)
H
2S(aq)+Fe
3+(aq)——Fe
2+(aq)+S(s)↓
Regenerative process: Fe
2+(aq)-2e---Fe
3+(aq) (cathodic reaction)
Have laboratory study to show, in the case of 15 DEG C of room temperatures, the soak time of 2 minutes, the specific absorption of hydrogen sulfide can reach 85%～92%, and is not subject to the impact of carbonic acid gas and ammonia.The regeneration stage completes at the electrolysis electrochemical inside reactor through peculiar set-up.
This method has following excellent feature: reproduction speed is fast, environment not being produced to dysgenic byproduct generates, molysite low price, reduce cost, can also utilize iron in slag as the supplementing of absorption agent, in the coagulation of sulphur, gravity based separation process, the loss of absorption agent affects the running cost of whole technique hardly.In addition, the links of whole technique is easily controlled.
3, biological desulphurization method
Biological desulphurization is a kind of new technology of instead of chemical desulfurization, and it can overcome the deficiency of chemical desulfurization aspect a lot.In biological desulphurization process, relate to two large quasi-microorganism, i.e. photosynthetic autotrophs microorganism and chemosynthetic autotroph microorganisms.
The thiobacterium that photosynthetic autotrophs microorganism mainly refers to contain photosynthetic pigments, can carry out luminous energy nutrition, they obtain energy from light, rely on the photosynthetic pigments in body, assimilate carbonic acid gas by photosynthesis.Photosynthetic autotrophs thiobacterium, can be with H in the time carrying out photosynthesis
2s is as assimilation CO
2hydrogen donor, H
2s is oxidized to sulphur or nearly oxidation step is sulfuric acid, and they are mostly anerobes, and the photosynthetic autotrophs microorganism of energy metabolism sulfide mainly has green sulfur bacteria and purple sulfur bacteria.Wherein, green sulfur bacteria is a kind of photosynthetic autotrophs microorganism of strictly anaerobic.The in the situation that of illumination and inorganic nutrient substance existence, green sulfur bacteria can utilize CO
2synthetic new cellular material, the desulfuration efficiency of this microorganism is high simultaneously, and meta-bolites elemental sulfur is released in outside, separates than being easier to.
But photosynthetic bacterium needs a large amount of radiating capacity in conversion process, on economic technology, be difficult to realize.Because generate in waste water after the microparticle of sulphur, be attached to extracellular, it is muddy that waste water will become, and transmittance will reduce greatly, thereby affect desulfuration efficiency.In addition, photosynthetic bacterium processing load is on the low side, and hydraulic detention time is long, requires the severe condition such as illumination and anaerobism, and progress is little, still the exploratory stage in batch test or laboratory lab scale.In addition, the relation existing between sweetening effectiveness and intensity of illumination is that illumination is not enough affects sweetening effectiveness, and illumination surplus causes SO
4 2-generation, only under the suitable condition of illumination, sulfide could be converted into elemental sulfur and completely without SO
4 2-produce, so, in employing green sulfur bacteria sweetening process, must strictly control reaction conditions.
Chemoautotrophic bacteria belongs to colorless sulfur bacteria (also comprising chemoheterotrophic bacteria), and wherein chemosynthetic autotroph microorganism is with CO
2for carbon source, simultaneously at oxidation S
2-process in obtain energy.In the situation that organic carbon source exists, the autotrophic microorganism of Partial Species can utilize organism carbon source to carry out heterotrophism metabolism.The thread sulphur bacteria that survives in Beggiatoa in sulfur-bearing water body and Thiothrix also can be by H
2s is oxidized to elementary sulfur, both can under the condition of aerobic, carry out, and also can under the condition of anaerobic, carry out.The in the situation that of aerobic, oxygen is as electron acceptor(EA), and the in the situation that of anaerobic, can utilize itrated compound as electron acceptor(EA).A lot of chemosynthetic autotroph microorganisms can be with elemental sulfur, H
2s, thiosulphate and organic sulfide are electron donor.
In the microbe groups of thiobacterium, be not that all thiobacteriums can both be used for sulfide oxidation.Because some thiobacterium accumulates the sulphur of generation in cell interior, varied bacteria growing also can cause the sludge bulking in reactor in addition, thereby affects the separation of elemental sulfur.If elemental sulfur can not be separated in time, just there is the problem of further oxidation, thereby affect desulfuration efficiency, so in the process of desulfurization unit operation, also must strictly control reaction conditions, to control the dominant growth of this quasi-microorganism.
1) Xie Er-Parker (Shell-Paques) desulfurization technology
The ultimate principle of its reaction of Xie Er-Parker (Shell-Paques) desulfurization technology technological principle is to contain H
2the biogas of S contacts with the soda water solution that contains chemosynthetic autotroph microorganism, H
2s by alkalescent menstruum after, generate elemental sulfur or vitriol through microorganism catalysis.
At present, Xie Er-Parker technique is one of desulfurization technology of global comparative maturity, has the following advantages: 1, safety: whole biological desulphurization system is closed operation, and H in biogas
2s is completely absorbed, the H not dissociating in the downstream of resorber
2s, does not have poisoning and injures and deaths event, non-environmental-pollution; 2, save: the desired less investment of this technology, its major equipment and instrument quantity are few.Running cost is low, produces required operator few, reduces human cost; Do not need chemical catalyst, biological catalyst can inactivation, and its autoregeneration, need not change, and required pharmaceutical chemicals in service is few, saves production cost; Running cost, the maintenance cost of this technique are all very low; 3, efficient: to use H in the Sweet natural gas after this technical guarantee desulfurization
2s content is less than 4ppmv; And turndown ratio is large, adapt to H
2s concentration range 50ppmv-100vol%, pressure range 1-100barg, has very high handiness, can adapt to H
2s peak load; 4, the technical process of this technology is simple, and Controlling System and Monitoring systems are little, there is no complicated control loop, and Operation and Maintenance is simple and convenient.Be applicable to containing H
2the small-sized gas field that S concentration is high, more economical, benefit is better; And use the device performance of this technology stable, and process, good in economic efficiency.
2) molysite organism-absorbing doctor treatment
The ultimate principle of molysite organism-absorbing doctor treatment is at absorption stage H
2s is by Fe
3+be oxidized to elemental sulfur, then under acidic conditions (pH=1.2～1.8) by the metabolism of thiobacillus ferrooxidant, by Fe
2+transform Fe
3+, and be recycled to absorption stage recycling.
Fe
3+there is quite high redox potential, can be by H
2s is converted into elemental sulfur, elemental sulfur can not be further oxidized to vitriol again.The elemental sulfur generating reclaims by after separating, Fe then
2+be Fe by thiobacillus ferrooxidant metabolism again
3+, and recycle.Therefore, most of researchists think that this method energy consumption is low, less investment, waste discharge are few, are more suitable for the process of biogas desulfurization.But in this method, need lower pH value (pH=1.2～1.8), need to add a large amount of acid to stablize pH, and the condition that thiobacillus ferrooxidant adapts to is harsher, cause the unstable of whole system to increase.
Under the strict condition of controlling oxygen supply, utilize chemosynthetic autotroph microorganism to remove the H in biogas
2s has very wide market application foreground, especially two stage desulfurization techniques, the precedent (Xie Er-Parker technique) that has had engineering to apply.This technique has the recycling that does not affect biogas, does not produce the features such as new environmental pollution.In addition, absorb H with molysite
2s, then, with bio-oxidation regeneration molysite absorption liquid, makes the method for molysite regeneration become in recent years new study hotspot.
Summary of the invention
The object of the present invention is to provide one to utilize collegen filament/polyester composite load Fe(III) remove the device and method of hydrogen sulfide in methane.In the present invention as the Fe(III of sweetening agent) can realize highly efficient regeneration, simultaneously can be by the H in biogas
2s is removed to below 0.5ppm.
In order to achieve the above object, collegen filament/polyester composite load Fe(III of utilizing of the present invention) remove the device of hydrogen sulfide in methane, comprise oxidizing tower and be filled with the absorption tower of collegen filament/polyester composite, on absorption tower, be respectively equipped with biogas entrance and remove the methane outlet after hydrogen sulfide, on oxidizing tower, offering respectively oxidizing gas entrance and oxidizing gas venting port; The second circulation fluid outlet on described oxidizing tower is connected with the entrance of the first circulation fluid on absorption tower, the first circulation fluid outlet on absorption tower is connected with settling tank, an outlet of settling tank is connected with elemental sulfur retrieving arrangement, and another outlet is connected with the second circulation fluid entrance on oxidizing tower.
Between the second circulation fluid entrance on another outlet and the oxidizing tower of described settling tank, be provided with recycle pump.
Described settling tank adopts inclined-plate clarifying basin.
Described elemental sulfur retrieving arrangement is filtering basin.
On described oxidizing tower, be also provided with the supplementary liquid entrance for supplementing source of iron.
Adopt this device to remove a method for hydrogen sulfide in methane, the circulation fluid in described device is the aqueous solution that contains source of iron, and the described method that removes hydrogen sulfide in methane comprises the following steps:
1) circulation fluid that exports out from the second circulation fluid enters absorption tower from the first circulation fluid entrance, and in this circulation fluid, contain Fe(III), Fe(III) carry out Coordination Adsorption with the carboxyl that has of collegen filament in collegen filament/polyester composite, Fe(III) be attracted on collegen filament, form and be present in the collegen filament/polyester composite Fe(III in adsorption tower with the form of filler) load;
2) when circulation fluid enters absorption tower, biogas enters in absorption tower from biogas entrance, hydrogen sulfide in biogas and collegen filament/polyester composite Fe(III) Fe(III in load) there is redox reaction, make the concentration of having reacted rear hydrogen sulfide in methane below 0.5ppm, then discharge from the methane outlet removing hydrogen sulfide; In redox processes, participate in the Fe(III of redox reaction) be converted into Fe(II), the hydrogen sulfide that participates in redox reaction is converted into elemental sulfur, Fe(II) and elemental sulfur along with circulation fluid is from the first circulation fluid outlet outflow absorption tower;
3) circulation fluid flowing out from absorption tower enters settling tank, and settling tank is separated the elemental sulfur in circulation fluid, and enters elemental sulfur retrieving arrangement by an outlet; And Fe(II) along with circulation fluid enters oxidizing tower from the second circulation fluid entrance from another outlet output of settling tank, simultaneously, air enters oxidizing tower from oxidizing gas entrance, Fe(II in circulation fluid) oxidation by air is Fe(III), then air is discharged from oxidizing gas venting port, contains Fe(III) circulation fluid from the second circulation fluid outlet output of oxidizing tower;
Fe(III in described step 1) in the first circulation fluid ingress circulation fluid) concentration is controlled at 0.1～0.8mol/L, the content of hydrogen sulfide in methane is at 50～5000ppm, and at one time in section, in described device, the flow of circulation fluid is per minute 5～50L, biogas enters absorption tower with the flow of per minute 1～100L from biogas entrance, and air enters oxidizing tower from oxidizing gas entrance with the flow of per minute 10～100L.
Described step 2) in make the temperature in absorption tower remain on 20～35 DEG C by the temperature that regulates biogas ingress biogas, described step 3) is by regulating the temperature of the second circulation fluid ingress circulation fluid to make the temperature in oxidizing tower remain on 20～35 DEG C.
In described step 3), circulation fluid enters oxidizing tower through recycle pump from the second circulation fluid entrance from another outlet output of settling tank; Described absorption tower is also provided with and supplements liquid entrance, when Fe(III in the first circulation fluid ingress circulation fluid on absorption tower) concentration be less than 0.1～0.8mol/L, supplement supplement liquid, make Fe(III in the first circulation fluid ingress circulation fluid) concentration be 0.1～0.8mol/L.
Described supplementary liquid and be ferric sulfate and/or ferric chloride in aqueous solution from the second circulation fluid exit circulation fluid out, and Fe(III in supplementary liquid) concentration be 1～3mol/L.
Compared with prior art, the present invention has following beneficial effect in the present invention:
First, what in absorption tower of the present invention, fill is collegen filament/polyester composite, this material is a kind of filler that connects microvoid structure that has, carboxyl in collegen filament/polyester composite on collegen filament and Fe(III) generation Coordination Adsorption, make the Fe(III in absorption tower) keep higher concentration, thus reach the effect of better absorbing hydrogen sulphide;
The second, collegen filament/polyester composite also has certain adsorption to hydrogen sulfide, makes to vulcanize Hydrogen Energy and is absorbed more fully in absorption tower, and profit in this way, can be by the H in biogas
2s is removed to below 0.5ppm;
The 3rd, collegen filament/polyester composite is to Fe(II) adsorption very little, in oxidizing tower, can realize Fe(III) highly efficient regeneration.
Further, whole system only need be supplemented the supplementary liquid of minute quantity, and without adding other consumable material, running cost is low.
Brief description of the drawings
Fig. 1 is setting drawing of the present invention;
Wherein, 1, oxidizing tower, 2, absorption tower, 3, inclined-plate clarifying basin, 4, recycle pump, 5, filtering basin, 6, collegen filament/polyester composite, 7, biogas entrance, 8, remove the methane outlet after hydrogen sulfide, 9, oxidizing gas entrance, 10, oxidizing gas venting port, 11, supplement liquid entrance.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further elaborated
Referring to Fig. 1, the present invention includes oxidizing tower 1 and be filled with collegen filament/polyester composite 6(preparation method referring to ZL201110287858.7, denomination of invention: a kind of preparation method of surface reaction type collagen fiber polyester composite) absorption tower 2, the bottom on absorption tower 2 offers respectively biogas entrance 7 and the outlet of the first circulation fluid, and top offers respectively the methane outlet 8 and the first circulation fluid entrance that remove after hydrogen sulfide; Bottom on oxidizing tower 1 offers respectively oxidizing gas entrance 9 and the second circulation fluid entrance, and oxidisability gas exhaust port 10 and the outlet of the second circulation fluid are arranged respectively at top, and side opening is provided with the supplementary liquid entrance 11 for supplementing source of iron; The second circulation fluid outlet on described oxidizing tower 1 is connected with the entrance of the first circulation fluid on absorption tower 2, the first circulation fluid outlet on absorption tower 2 is connected with inclined-plate clarifying basin 3, an outlet of inclined-plate clarifying basin 3 is connected with the filtering basin 5 for reclaiming elemental sulfur, and another outlet is connected with the second circulation fluid entrance on oxidizing tower 1 through recycle pump 4.
The present invention gives and utilizes collegen filament/polyester composite load Fe(III) device that the removes hydrogen sulfide in methane method that removes hydrogen sulfide in methane comprises the following steps:
1) circulation fluid that exports out from the second circulation fluid of oxidizing tower 1 tower top is for containing Fe(III) aqueous solution, and Fe(III) concentration be 0.1～0.8mol/L, this circulation fluid enters absorption tower 2 from the first circulation fluid entrance of absorption tower 2 tower tops, the Fe(III wherein containing) carry out Coordination Adsorption with the carboxyl that has of collegen filament in collegen filament/polyester composite 6, Fe(III) be attracted on collegen filament, form and be present in the collegen filament/polyester composite Fe(III in adsorption tower 2 with the form of filler) load;
2) when circulation fluid enters absorption tower 2, biogas enters in absorption tower 2 from the biogas entrance at the bottom of 2 towers of absorption tower, hydrogen sulfide in biogas and collegen filament/polyester composite Fe(III) Fe(III in load) there is redox reaction, make the concentration of having reacted rear hydrogen sulfide in methane below 0.5ppm, then discharge from the methane outlet removing hydrogen sulfide; In redox processes, participate in the Fe(III of redox reaction) be converted into Fe(II), participate in the hydrogen sulfide of redox reaction and be converted into elemental sulfur, Fe(II) and elemental sulfur along with circulation fluid is from the first circulation fluid outlet outflow absorption tower 2 at the bottom of 2 towers of absorption tower; Wherein, the content of hydrogen sulfide in methane, at 50～5000ppm, regulates the temperature of biogas ingress biogas to make the temperature in absorption tower 2 remain on 20～35 DEG C;
3) circulation fluid that goes out to flow out from absorption tower 2 tower bottom flows enters inclined-plate clarifying basin 3, and inclined-plate clarifying basin 3 is separated the elemental sulfur in circulation fluid, and enters filtering basin 5 by an outlet; And Fe(II) along with circulation fluid enters oxidizing tower 1 through recycle pump 4 from the second circulation fluid entrance at the bottom of oxidizing tower 1 tower from another outlet output of inclined-plate clarifying basin 3, simultaneously, air enters oxidizing tower 1 from the oxidizing gas entrance at the bottom of oxidizing tower 1 tower, Fe(II in circulation fluid) oxidation by air is Fe(III), then air is discharged from oxidizing gas venting port, contains Fe(III) circulation fluid from the second circulation fluid outlet output of oxidizing tower 2 tower tops; Wherein, regulate the temperature of the second circulation fluid ingress circulation fluid to make the temperature in oxidizing tower 1 remain on 20～35 DEG C;
In section, the flow of the circulation fluid moving in apparatus of the present invention is per minute 5～50L at one time, and biogas ingress biogas flow is per minute 1～100L, and air is per minute 10～100L at oxidizing gas inlet flow rate.
In addition, when Fe(III in the second circulation fluid exit circulation fluid on absorption tower 2) concentration be less than 0.1～0.8mol/L, supplement and contain Fe(III from the supplementary liquid entrance on absorption tower) the aqueous solution, and Fe(III) concentration is 1～3mol/L, makes Fe(III in the first circulation fluid ingress circulation fluid) concentration be 0.1～0.8mol/L.
Concrete, circulation fluid and supplementary liquid that the present invention exports out from the second circulation fluid of oxidizing tower 1 tower top are ferric sulfate aqueous solution or ferric chloride in aqueous solution, can be also the formulated mixing solutionss that adds water after the ferric sulfate that is 3:1 by mass ratio and iron(ic) chloride mix.
Below in conjunction with accompanying drawing, the present invention is described in further details to explanation, the method that the present invention removes hydrogen sulfide in methane comprises the following steps:
Referring to Fig. 1,1) circulation fluid that exports out from the second circulation fluid of oxidizing tower 1 tower top is Fe(III) the concentration ferric chloride in aqueous solution that is 0.6mol/L, this circulation fluid enters absorption tower 2 from the first circulation fluid entrance of absorption tower 2 tower tops, the Fe(III wherein containing) carry out Coordination Adsorption with the carboxyl that has of collegen filament in collegen filament/polyester composite 6, Fe(III) be attracted on collegen filament, form and be present in the collegen filament/polyester composite Fe(III in adsorption tower 2 with the form of filler) load;
2) when circulation fluid enters absorption tower 2, biogas enters in absorption tower 2 from the biogas entrance at the bottom of 2 towers of absorption tower, hydrogen sulfide in biogas and collegen filament/polyester composite Fe(III) Fe(III in load) there is redox reaction, make the concentration of having reacted rear hydrogen sulfide in methane below 0.5ppm, then discharge from the methane outlet removing hydrogen sulfide; In redox processes, participate in the Fe(III of redox reaction) be converted into Fe(II), participate in the hydrogen sulfide of redox reaction and be converted into elemental sulfur, Fe(II) and elemental sulfur along with circulation fluid is from the first circulation fluid outlet outflow absorption tower 2 at the bottom of 2 towers of absorption tower; Wherein, the content of hydrogen sulfide in methane, at 100ppm, regulates the temperature of biogas ingress biogas to make the temperature in absorption tower 2 remain on 35 DEG C;
3) circulation fluid that goes out to flow out from absorption tower 2 tower bottom flows enters inclined-plate clarifying basin 3, and inclined-plate clarifying basin 3 is separated the elemental sulfur in circulation fluid, and enters filtering basin 5 by an outlet; And Fe(II) along with circulation fluid enters oxidizing tower 1 through recycle pump 4 from the second circulation fluid entrance at the bottom of oxidizing tower 1 tower from another outlet output of inclined-plate clarifying basin 3, simultaneously, air enters oxidizing tower 1 from the oxidizing gas entrance at the bottom of oxidizing tower 1 tower, Fe(II in circulation fluid) oxidation by air is Fe(III), then air is discharged from oxidizing gas venting port, contains Fe(III) circulation fluid from the second circulation fluid outlet output of oxidizing tower 2 tower tops; Wherein, regulate the temperature of the second circulation fluid ingress circulation fluid to make the temperature in oxidizing tower 1 remain on 25 DEG C;
In section, the flow of the circulation fluid moving in apparatus of the present invention is per minute 10L at one time, and biogas ingress biogas flow is per minute 24L, and air is per minute 50L at oxidizing gas inlet flow rate.
In addition, when Fe(III in the second circulation fluid exit circulation fluid on absorption tower 2) concentration be less than 0.6mol/L, supplement Fe(III from the supplementary liquid entrance on absorption tower) ferric chloride in aqueous solution that concentration is 1.5mol/L, make Fe(III in the first circulation fluid ingress circulation fluid) concentration be 0.6mol/L.
Claims (2)
1. one kind is utilized collegen filament/polyester composite load Fe(III) remove the device of hydrogen sulfide in methane, it is characterized in that: comprise oxidizing tower (1) and be filled with the absorption tower (2) of collegen filament/polyester composite (6), on absorption tower (2), be respectively equipped with biogas entrance (7) and remove the methane outlet (8) after hydrogen sulfide, on oxidizing tower (1), offer respectively oxidizing gas entrance (9) and oxidizing gas venting port (10); The second circulation fluid outlet on described oxidizing tower (1) is connected with the entrance of the first circulation fluid on absorption tower (2), the first circulation fluid outlet on absorption tower (2) is connected with settling tank, an outlet of settling tank is connected with elemental sulfur retrieving arrangement, and another outlet is connected with the second circulation fluid entrance on oxidizing tower (1);
Between the second circulation fluid entrance on another outlet and the oxidizing tower (1) of described settling tank, be provided with recycle pump (4);
Described elemental sulfur retrieving arrangement is filtering basin (5);
On described oxidizing tower (1), be also provided with the supplementary liquid entrance (11) for supplementing source of iron.
2. collegen filament/polyester composite load Fe(III of utilizing according to claim 1) remove the device of hydrogen sulfide in methane, it is characterized in that: described settling tank adopts inclined-plate clarifying basin (3).
3. adopt device described in claim 1 to remove a method for hydrogen sulfide in methane, it is characterized in that, the circulation fluid in described device is the aqueous solution that contains source of iron, and the described method that removes hydrogen sulfide in methane comprises the following steps:
1) circulation fluid that exports out from the second circulation fluid enters absorption tower (2) from the first circulation fluid entrance, and in this circulation fluid, contain Fe(III), Fe(III) carry out Coordination Adsorption with the carboxyl that has of collegen filament in collegen filament/polyester composite (6), Fe(III) be attracted on collegen filament, form with the form of filler and be present in the collegen filament/polyester composite Fe(III in absorption tower (2)) load;
2) when circulation fluid enters absorption tower (2), biogas enters in absorption tower (2) from biogas entrance (7), hydrogen sulfide in biogas and collegen filament/polyester composite Fe(III) Fe(III in load) there is redox reaction, make the concentration of having reacted rear hydrogen sulfide in methane below 0.5ppm, then discharge from the methane outlet (8) removing hydrogen sulfide; In redox processes, participate in the Fe(III of redox reaction) be converted into Fe(II), the hydrogen sulfide that participates in redox reaction is converted into elemental sulfur, Fe(II) and elemental sulfur along with circulation fluid is from the first circulation fluid outlet outflow absorption tower (2);
3) circulation fluid that flow out (2) from absorption tower enters settling tank, and settling tank is separated the elemental sulfur in circulation fluid, and enters elemental sulfur retrieving arrangement by an outlet; And Fe(II) along with circulation fluid enters oxidizing tower (1) from the second circulation fluid entrance from another outlet output of settling tank, simultaneously, air enters oxidizing tower (1) from oxidizing gas entrance (9), Fe(II in circulation fluid) oxidation by air is Fe(III), then air is discharged from oxidizing gas venting port (10), contains Fe(III) circulation fluid from the second circulation fluid outlet output of oxidizing tower (1).
4. the method that removes hydrogen sulfide in methane according to claim 3, it is characterized in that: the Fe(III in described step 1) in the first circulation fluid ingress circulation fluid) concentration is controlled at 0.1 ~ 0.8mol/L, the content of hydrogen sulfide in methane is at 50 ~ 5000ppm, and at one time in section, in described device, the flow of circulation fluid is per minute 5 ~ 50 L, biogas enters absorption tower (2) with the flow of per minute 1 ~ 100L from biogas entrance (7), and air enters oxidizing tower (1) from oxidizing gas entrance (9) with the flow of per minute 10 ~ 100 L.
5. the method that removes hydrogen sulfide in methane according to claim 3, it is characterized in that: described step 2) in make the temperature in absorption tower (2) remain on 20 ~ 35 DEG C by the temperature that regulates biogas ingress biogas, described step 3) is by regulating the temperature of the second circulation fluid ingress circulation fluid to make the temperature in oxidizing tower (1) remain on 20 ~ 35 DEG C.
6. the method that removes hydrogen sulfide in methane according to claim 3, is characterized in that: in described step 3), circulation fluid enters oxidizing tower (1) through recycle pump (4) from the second circulation fluid entrance from another outlet output of settling tank; Described absorption tower is also provided with and supplements liquid entrance (11), when Fe(III in the first circulation fluid ingress circulation fluid of absorption tower (2)) concentration be less than 0.1 ~ 0.8mol/L, supplement supplement liquid, make Fe(III in the first circulation fluid ingress circulation fluid) concentration be 0.1 ~ 0.8mol/L.
7. the method that removes hydrogen sulfide in methane according to claim 6, it is characterized in that: described supplementary liquid and be ferric sulfate and/or ferric chloride in aqueous solution from the second circulation fluid exit circulation fluid out, and Fe(III in supplementary liquid) concentration be 1 ~ 3mol/L.
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| CN114181749B (en) * | 2021-12-27 | 2022-09-20 | 华夏碧水环保科技股份有限公司 | Two-section type biogas biological desulfurization device |
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