CN100450917C - Method for recovering sulfur and making hydrogen from hydrogen sulfide - Google Patents

Method for recovering sulfur and making hydrogen from hydrogen sulfide Download PDF

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CN100450917C
CN100450917C CNB2006100580638A CN200610058063A CN100450917C CN 100450917 C CN100450917 C CN 100450917C CN B2006100580638 A CNB2006100580638 A CN B2006100580638A CN 200610058063 A CN200610058063 A CN 200610058063A CN 100450917 C CN100450917 C CN 100450917C
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absorption
liquid
gas
reactor
hydrogen
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CNB2006100580638A
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CN101028920A (en
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俞英
黄海燕
李发永
曹作刚
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中国石油大学(北京)
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Abstract

A process for recovering sulfur and preparing H2 from the hydrogen sulfide at same time is characterized by that an internal circulation absorption type reactor and an electrolyzing reactor with dual electrode plates are simultaneously used for the oxidizing absorption reaction and electrolytic regeneration reaction.

Description

While recovery sulphur and the method for producing hydrogen from stink damp
Technical field
The present invention relates to the method for recovery sulphur and hydrogen from hydrogen sulfide, relate in particular to and a kind of absorbing hydrogen sulphide gas technology is combined with the indirect electrolytic technology, realize producing simultaneously the method for sulphur and hydrogen by the recycle of absorption agent.
Background technology
When the secondary processing of sulphur-bearing crude, the sulfide major part in the crude oil changes into hydrogen sulfide, if be present in the refinery exhaust. and not treated and directly refinery exhaust is discharged in the atmosphere to these hydrogen sulfide, can cause serious environmental to pollute.Increase and national pay attention to day by day along with the high-sulpur crude amount of finish to environmental protection work; particularly high in recent years sulfur-bearing gas field constantly occurs; (content as hydrogen sulfide in the Sweet natural gas ore deposit, Weiyuan, Sichuan is about 4.8%; the content of hydrogen sulfide is up to more than 90% in the Hebei Zhao Lan celebrating natural gas in oil and gas fields), H 2The handling problem of S more and more causes people's attention.
The method that removes hydrogen sulfide is varied, in order to recycle the sulphur in the hydrogen sulfide, the oxidation style that adopted are oxidized to the effect that elemental sulfur reaches the purification hydrogen sulfide tail gas to hydrogen sulfide more, oxidation style generally is used for higher waste gas of sulphur content and liquid waste disposal, but the technology that wherein occupy dominant position still is Claus method (claiming Kraus process again), come recovery sulphur from magnetization hydrogen by at present industrial generally employing, the Claus method at first uses weakly alkaline organic amine to the H in the sour gas 2S carries out absorbing and removing, and by the H of steam stripping regeneration organic amine with the acquisition higher concentration 2S is then with a part of H 2S is oxidized to SO 2, again with SO 2With H 2S water generation reaction and sulphur.The Claus method is updated in practice, has developed COPE (oxygen enrichment claus process), Superclaus (super Crouse) technology, fluidized-bed claus process etc.The Lo-Cat method (" wet method ") that the eighties produces then absorbs and oxidation H with EDTA and many aldehyde radicals sugar complexing ferrous solution 2S, solution is with air regenesis.
Oxidation style removal efficiency height and speed are fast, are applicable to the H that sulphur content is higher, concentration is bigger 2The purification of S tail gas or sour water also needs pending gas is handled in advance with enrichment hydrogen sulfide content wherein usually, needs extra operation and equipment.In addition, in the operation of claus process, require to keep H 2S: SO 2(mol ratio) is 2: 1, requires the control proper temperature simultaneously in case there is liquid phase to condense (agglomerative liquid phase meeting strong corrosion equipment) in the system, also needs to install mist eliminator and removes sulphur in the air-flow, improves the sulfur recovery amount simultaneously.
Another kind of oxidation style is the selective oxidation method, utilizes suitable catalyst action wherein H 2The S direct oxidation is a sulphur, and reaction process is H 2S+1/2O 2=1/x S x+ H 2O, the key of this method success be to develop selectivity good, to H 2O and excessive O 2All insensitive high activated catalyst.For example the different mixtures with the ferrous metals oxide compound prepares high price iron (VI) salt, martial ethiops etc., and the removal efficiency of selective oxidation can reach 98%-99%.
More than various traditional methods improve in any case, its research emphasis is all absorbing and recovery sulphur hydrogen sulfide, has only utilized H 2Element sulphur among the S, protium then are transformed into water.
Traditional method is unfavorable for the comprehensive utilization of resource, makes hydrogen sulfide decompose the design philosophy appearance that recovery sulphur is produced hydrogen simultaneously so just had, as: pyrolysis method, photodissociation method, electrolytic process etc.Wherein electrolytic process can be divided into direct electrolysis method and indirect electrolytic method again.Though the direct electrolysis method less energy intensive generates the sulphur of segregative crystalline state, sulphur can be deposited on electrode surface in a large number, causes the anodic passivation, and greatly reduced electrode life.For fear of this problem, investigators have proposed the indirect electrolytic method again, utilize exactly a kind of in the middle of the circulation agent with hydrogen sulfide absorption, produce sulphur, again with the absorption liquid electrolysis, produce hydrogen after the separation, simultaneously in the middle of the circulation agent be reduced in addition recycle.
Kalina and Mass[Int.J.Hydrogen Energy 198510 (3)] with iodide ion to H 2The S aqueous solution carries out oxidation, generates sulphur and HI.HI solution is handled with electrochemical method and is generated hydrogen and iodonium ion.This technology can be avoided the anode passivation problem that sulphur causes in the direct electrolysis method, but because sedimentary sulfur purity is bad, contains iodide ion in the sulphur, need reclaim iodine with alcohol, and sulphur also need carry out recrystallization through toluene can reach 99.3%.
The eighties Japan scientist Fuji has proposed to be the hydrogen sulfide desulfurization process for making hydrogen of representative, to adopt Fe with Fe (III) salt strongly-acid sweetening agent 3+/ Fe 2+Make the oxidation absorption agent, the indirect electrolytic method is produced hydrogen and sulphur by hydrogen sulfide.Japanese Patent JP 58,181 has discussed among the JP706/1983 at 65 ℃, 18g FeCl 3In the solution, fed hydrogen sulfide 5 minutes with the speed of 200ml/min, the productive rate of sulphur reaches 95%.Oxidation of divalent iron ion after will reducing again with electrolytic method then becomes ferric ion to send absorption reactor thermally back to, and in the negative electrode recover hydrogen.The advantage of this method is that the speed of absorbing hydrogen sulphide is fast, but the sulfur granule that generates is too tiny, is difficult to Separation and Recovery, so the rate of recovery and purity are all not high.
Japan scholar Fuji[Ind.Eng.Chem.Res, 1991,30] once reported a kind of method that is suitable for handling the magnetization hydrogen of a large amount of high densitys.This method is that hydrogen sulfide is by FeCl when temperature is 70 ℃ 3Solution oxide absorbs, and produces sulphur, and productive rate is almost 100%.To the Fe that generates 2+Solution carries out electrolysis, and current density is 100mAcm -2The time, producing hydrogen, electrolyzer is pressed and is 0.7V.Use therein FeCl 3Solution is after by a large amount of HCl acidifyings, guaranteeing that reaction is to carry out under strong acid condition.The device of absorbing hydrogen sulphide adopts bubble tower in this method, and hydrogen sulfide is imported by the cup-shaped gas operated device of a rotation, this system to the specific absorption of hydrogen sulfide absorption be 99%, hydrogen manufacturing power consumption 2.0kWh/m 3H 2(mark).Think that in the industry the economy of this method is expected to compare with Kraus process, but the sulphur that this method obtains is the mucus shape, is difficult to reclaim, really be used for the industrialization operation and also need further supporting technology and device.
Japan scholar Noguchi, people such as Hiroshi propose a novel method in European patent EP 0 348 875, the oxidation absorption temperature of hydrogen sulfide is brought up to more than the fusing point of sulphur, make sulphur separated under the fused state.They think that absorption agent uses FeCl 3Better with the HCl mixed aqueous solution, Fe 3+Concentration is 0.1-5mol/Kg (water), H +Concentration is 0.5-15mol/Kg (water), is lower than absorbing hydrogen sulphide under 150 ℃ of temperature being higher than 120 ℃.Under high like this temperature, the sulphur of various crystal formations all melts, thereby is convenient to separate, and can obtain higher purity again.But not adopting this method in the pilot experiment of Japan, mainly is this technology has increased equipment under High Temperature High Pressure corrosion, and refinery's hydrogen sulfide needs pressurization, increases problem such as energy consumption and is difficult to solve.
Present technology adopts the bubbling mode that gas is fed absorption liquid from the resorber bottom in absorption and oxidation to hydrogen sulfide more.Common absorption reactor thermally 10 generally is made of the nozzle 12 in reaction tubes 11 and this reaction tubes of insertion, and as shown in Figure 1, the top of reaction tubes 11 is provided with liquid inlet 111, and the bottom is provided with liquid exit 112; Nozzle 12 is used for gas is imported in the reaction tubes, so the upper end is gas inlet 121, the lower end is a pneumatic outlet, and this nozzle inserts from reaction tubes 11 tops, the major part of nozzle all is placed in the reaction tubes 11, and makes the bottommost of exit end and reaction tubes keep a segment distance.Add absorption liquid during operation earlier from liquid inlet 111 in reaction tubes 11, feed hydrogen sulfide containing gas by nozzle 12 in reaction tubes then, the bottom contacts with absorption liquid and reacts in reaction tubes, and hydrogen sulfide is absorbed to generate sulphur.Reacted liquid and sulphur are emitted from exporting 112, and unnecessary tail gas can be discharged from reactor top.Since oxidation form the easy plug nozzle of sulfur granule (the meticulous or thickness of particle), so present operation all is an intermittent type, is difficult to really realize continuous high-efficient absorbing hydrogen sulphide recovery sulphur and produces hydrogen simultaneously.And result of study shows that gas-to-liquid contact is abundant inadequately in such absorption operation, and the specific absorption of hydrogen sulfide is difficult to reach 100%, still can contain higher hydrogen sulfide in the tail gas.
In addition, for sulfide hydrogen sour gas, hydrogen sulfide content and with the impurity composition of hydrogen sulfide coexistence etc. certain requirement is arranged all in the present technology implementation, be subjected to certain limitation in actual applications.
Summary of the invention
Subject matter to be solved by this invention is exactly to research and propose a kind ofly to realize that from hydrogen sulfide recovery sulphur produces the method for hydrogen simultaneously, in operating process, unite and adopted absorption reactor thermally and electrolysis reactor, the absorption oxidizing reaction of hydrogen sulfide is combined with the electrolytic regeneration technology of absorption liquid, change the operating method of prior art, alleviate sulphur and generate the obstruction of back absorption reactor thermally, make whole process can realize continuous operation, improve utilization ratio the hydrogen sulfide resource.
The present invention has provided on the other hand and has adopted a kind of internal-circulation type absorption reactor thermally and bipolar board-like electrolysis reactor associating, change the gas-to-liquid contact condition, realization recovery sulphur from hydrogen sulfide is produced the continuous process flow process of hydrogen simultaneously, and applicable to handling the bigger unstripped gas of hydrogen sulfide content variation range.
According to provided by the invention from H 2 S-containing gas recovery sulphur and produce the method for hydrogen simultaneously, it comprises: adopt the absorption liquid that contains ferric ion in absorption reactor thermally hydrogen sulfide to be oxidized to sulphur, and ferric ion that will be wherein is to send into electrolysis reactor as anolyte after absorption liquid that part is reduced to ferrous ion is isolated sulphur at least, recycle for absorption reactor thermally through electrolytic regeneration, produce hydrogen from the negative electrode of electrolysis reactor simultaneously; Wherein, when the control absorption liquid enters absorption reactor thermally through nozzle H 2 S-containing gas is brought into, and control liquid/gas volume ratio is about 3-10.
The method according to this invention, fully contact the rate of recovery that improves sulphur for what realize absorption liquid and stink damp, in the process of absorbing hydrogen sulphide gas recovery sulphur, make absorption liquid in flow process, bring hydrogen sulfide containing gas into absorption reactor thermally simultaneously through nozzle, make absorption liquid in the reaction tubes of reactor, contact and mix and make the gas-liquid mixture of formation in reactor, form circulation with gas.
In the method for the present invention, described absorption liquid is an acid system, and ferric ion concentration was preferably greater than 0.18 mol when it entered absorption reactor thermally, and negatively charged ion is chlorion or sulfate ion, the process of absorbing hydrogen sulphide oxidation recovery sulphur is a normal pressure, service temperature 20-80 ℃.
Preferably, described absorption liquid consists of Fe 2+Concentration 0.3-0.7M, Fe 3+Concentration 0.3-0.8M, H +Concentration 2-10M (HCl system and/or H 2SO 4System).
The concentration of stink damp is 2-100% in the accessible H 2 S-containing gas of the inventive method.That is, for the lower sour gas of hydrogen sulfide content and do not require and to carry out enrichment earlier.This gas can be high pressure gas or low-pressure gas.
The method according to this invention, the process that absorbing hydrogen sulphide gas and oxidation generate sulphur adopts the absorption reactor thermally that can realize liquid stream internal recycle, preferably, the reaction tubes top of this absorption reactor thermally is provided with the nozzle of being made up of interior pipe and sleeve pipe, the interior pipe of this nozzle is a hollow tube, the upper end is the liquid inlet, the lower end is liquid spraying outlet and the reaction tubes import that is positioned at absorption reactor thermally top, casing pipe sleeve is located at outside the interior pipe, be sealing between top and outer wall of inner tube, the bottom then with extraneous conducting, form annular space between sleeve pipe and the interior pipe, and this sleeve pipe sidewall also is provided with the gas inlet that communicates with annular space; During operation absorption liquid is added the reaction tubes that sprays into reactor by outlet from the liquid inlet of interior pipe, H 2 S-containing gas is fed from the gas inlet, be absorbed liquid through annular space and in flow process, carry the reaction tubes that enters reactor.
The method according to this invention, the reaction tubes top of described absorption reactor thermally and bottom are respectively equipped with first liquid discharge outlet and second liquid discharge outlet, be arranged with the inner catheter that two-port all is conducted with reaction tubes in the described reaction tubes, and this inner catheter is arranged between two liquid discharge outlets of reaction tubes, and the liquid exit of nozzle just is positioned at inner catheter upper port top, the gas that absorption liquid is carried from annular space when nozzle sprays enters inner catheter, descending along inner catheter in gas-to-liquid contact, and, form internal recycle from the up upper port that enters inner catheter once more of the interlayer between reaction tubes and the inner catheter.The present invention claims that this absorption reactor thermally is an internal-circulation type jet-type absorption reactor thermally.
Preferred version of the present invention is to adopt above-mentioned internal-circulation type jet-type absorption reactor thermally, make absorption liquid enter inner catheter through pipe inspection in the nozzle, the absorption liquid that by nozzle sprayed during through annular space sleeve pipe and interior pipe between from the gas of orifice gas inlet this moment carries and while sucting reaction device inner catheter, descending with absorption liquid along inner catheter, and return the up inner catheter that enters once more of interlayer between reaction tubes and inner catheter from the reaction tubes lower end, stink damp fully contacts with absorption liquid and is oxidized to sulphur (elemental sulfur) in working cycle, by this redox reaction, sulphur constantly generates in absorption liquid, and the ferric ion in the absorption liquid is reduced to ferrous ion (absorption liquid of this moment claims to treat regenerated liquid).
According to aforesaid method of the present invention, in the working cycle, emitting wherein ferric ion from first liquid discharge outlet on absorption reactor thermally top is reduced to the absorption liquid of ferrous ion to small part (this liquid effluent is a large amount of, wherein contain the elemental sulfur that is settled out), send into electrolysis reactor as anolyte behind the Separation and Recovery sulphur wherein, in electrolytic process, be oxidized to the absorption liquid that contains ferric ion and return absorption reactor thermally, and collect the hydrogen that discharges from negative electrode in the electrolytic process.
According to response situation, can be simultaneously or to emit wherein ferric ion from second liquid discharge outlet of absorption reactor thermally bottom at any time be that part is reduced to the absorption liquid of ferrous ion (this absorption liquid to be regenerated is a spot of at least, but sulphur content wherein is than higher), send into electrolysis reactor as anolyte behind the Separation and Recovery sulphur, in electrolytic process, be oxidized to the absorption liquid that contains ferric ion and return absorption reactor thermally, collect the hydrogen that discharges from negative electrode in the electrolytic process.
In the method for the present invention, the sulphur solid particulate that gas liquid reaction generates away from the liquid exit of nozzle, can effectively avoid the situation of plug nozzle to produce owing to Circulation, and the circulation of gas-liquid mixed stream has also prolonged gas-liquid contact time, so the inventive method can realize H 2The S specific absorption greater than 99% and sulfur purity greater than 99.8% good result.Treat that sulphur in the regenerated liquid can adopt and filter or centrifugal separation method separates and collects.
The method according to this invention, treat that from what absorption reactor thermally was discharged regenerated liquid carries out sending into electrolysis reactor as anolyte behind the Separation and Recovery sulphur, in electrolytic process, be oxidized to the absorption liquid that contains ferric ion and return absorption reactor thermally, collect the hydrogen that discharges from negative electrode simultaneously.
The method according to this invention is implemented the process of electrolytic recovery and is adopted bipolar board-like electrolysis reactor the regenerated liquid for the treatment of behind the separation sulphur.Described bipolar board-like electrolysis reactor is meant that anolyte (treating regenerated liquid) enters through different inlets with catholyte (electrolytic solution), in electrolyzer, has runner separately, do not go here and there a kind of electrolysis reactor of liquid phenomenon in the whole electrolytic process, can guarantee the regeneration of absorption liquid.Described bipolar board-like electrolysis reactor can have different project organizations, as long as can realize can separately flowing and can using from dipolar electrolytic solution, can adopt any reactor that discloses or be purchased, also can the specialized designs manufacturing.That is, the present invention preferably uses and can realize that anolyte and catholyte separately flow therein, and crossfire or blended electrolysis reactor do not take place in electrolytic process.For example, the applicant has obtained a kind of bipolar board-like electrolysis reactor (patent No.: ZL2004 2 0047897.5) of China Patent Right, the import and the outlet of two electrolytic solution are set respectively on the fixed charge method end plate of the two ends of electrolyzer, electrolyzer adopts bipolar graphite current collecting board element, the SPE electrode is alternately arranged and is constituted, the SPE electrode can be by Graphite cloth, ion-exchange membrane (Nafion film) and platinum plating Graphite cloth constitute, the two sides of each bipolar graphite current collecting board element have been designed cathode flow channels and anode flow channel respectively, like this, adopt the bifilar discharging of bifilar charging in the electrolytic process, and two strands of materials can not mix in electrolyzer.At this this full patent texts content is introduced the present invention, no longer be repeated in this description for saving space.
Fig. 2 has illustrated the principle of the inventive method: hydrogen sulfide containing sour gas enters absorption reactor thermally, hydrogen sulfide in absorbing (oxidation) reactor by Fe 3+(with Fe 3+/ Fe 2+Be middle circulation agent) oxidation generation sulphur (elemental sulfur), Fe simultaneously 3+Also be reduced to Fe 2+After sulphur is separated, contain H +And Fe 2+Reaction solution (treating regenerated liquid) be sent to electrolysis reactor, at anode Fe 2+Be oxidized to Fe 3+, then send absorption reactor thermally back to and recycle H +Passing ion-exchange membrane enters negative electrode and is reduced to H 2The reaction of whole process is as follows:
In the absorption reactor thermally: 2Fe 3++ H 2S=2Fe 2++ 2H ++ S ↓
In the electrolysis reactor:
Anode: 2Fe 2+=2Fe 3++ 2e
Negative electrode: 2H ++ 2e=H 2
Electrolysis reactor total reaction: 2Fe 2++ 2H +=2Fe 3++ H 2
Cooperate the associating (double-reactor) of preferred internal-circulation type absorption reactor thermally of the present invention and bipolar plates electrolysis reactor to use, can make above process realize operate continuously, removal of hydrogen sulfide makes high purity sulphur and hydrogen when polluting.
What absorb sweetening agent among the present invention consists of the small molecules mineral compound, and chemical stability is better, does not have the degraded Problem of Failure, and loss is less in absorptions-regenerative process.
Among the present invention owing to adopted the absorption liquid (being higher than 0.18M) of high Fe (III) content, so sweetening agent sulfur capacity (being about the Lo-Cat method more than 10 times) greatly, can the power consumption of corresponding reduction doctor solution round-robin.
Absorption liquid is to H among the present invention 2The absorption of S has very strong selectivity, with H 2The CO of S coexistence 2The absorption of system is not exerted an influence with hydrocarbon gas.
The method according to this invention, in the time of regeneration of absorption solution, but the highly purified hydrogen of low power consumption ground by-product (the hydrogen manufacturing power consumption is than water electrolysis hydrogen producing low 1/3~1/2) has not only improved H 2The resource utilization of S, and the H of by-product 2Can be used as the additional raw material of hydrogenating desulfurization.
Just be based on above advantage, the present invention utilizes double-reactor method of recovery sulphur and hydrogen from hydrogen sulfide to prove it is feasible technically by experiment, particularly at the H that is difficult for the Claus method reclaiming 2The S unstripped gas, this method will show bigger superiority.In the existing developmental stage of China, middle and small scale enterprise can not bear the bigger investment of Claus method mostly, and the popularization of the inventive method should have the potential application prospect.
In a word, the present invention is the applicant has carried out comprehensive further investigation in recent years to art technology result, utilize the associating of double-reactor in the technical process, by improvement to the absorption reaction process, adopt spouting of liquid to bring gas into absorption reactor thermally, and alleviated sulphur plug nozzle phenomenon by Circulation; Bipolar board-like electrolysis reactor has been introduced solid electrolyte electrode (SPE) technology, helps the separation of gas.So, the present invention has critical breakthrough in the hydrogen balance of the serialization that utilizes hydrogen sulfide hydrogen manufacturing, hydrogen sulfide hydrogen production process and the aspects such as circulation of absorption liquid than prior art, especially this method does not have particular requirement for the content of stink damp, for high density H 2S (>90%) and low H 2The H of S content (2%) sour gas 2The S selectivity absorbs, and all receives better effects, and this method is to containing H 2The flow of S sour gas and and H 2The requirement of the impurity composition of S coexistence etc. is all tolerant, technical process is simple, the operational condition gentleness, sweetening effectiveness is (to a specific absorption height of hydrogen sulfide) better, more help improving utilization ratio to the hydrogen sulfide resource, the technology of double-reactor associating also all provides the approach of economic environmental protection simultaneously to reclaiming hydrogen and the sulphur in the hydrogen sulfide for hydrogen sulfide treatment.
Absorption liquid of the present invention is through directly recycle of electrolytic regeneration, the periodical operation of haveing no alternative but adopt of the prior art improved and optimizated to can realizing that recovery sulphur produces the continuous operation of hydrogen simultaneously, thereby have more practicality in industrialization is operated.
The accompanying drawing summary
The absorption reactor thermally synoptic diagram that Fig. 1 adopts for prior art.
Fig. 2 produces the principle schematic of hydrogen simultaneously for the present invention adopts double-reactor recovery sulphur from hydrogen sulfide.
Fig. 3 is an internal-circulation type jet-type absorption reactor thermally structural representation of the present invention.
Fig. 4 is structure of nozzle figure in the internal-circulation type jet-type absorption reactor thermally of Fig. 3.
Fig. 5 produces the process flow sheet of hydrogen simultaneously for the present invention adopts double-reactor recovery sulphur from hydrogen sulfide.
Fig. 6 is the graphic representation that air input influences specific absorption when adopting the inventive method.
Fig. 7 is the graph of relation that concentration of absorbing influences specific absorption when adopting the inventive method.
Fig. 8 is the change curve of Fe (II) concentration in the operation process that adopts the inventive method.
Fig. 9 is the change curve of HCl concentration in the operation process that adopts the inventive method.
Figure 10 is hydrogen sulfide absorption rate and absorption rate change curve in the reaction process that adopts the inventive method.
Figure 11 is the change curve of electrolytic hydrogen production speed and power consumption in the operation process that adopts the inventive method.
Embodiment
Below in conjunction with specific embodiment detailed description the present invention program's realization, be intended to help the reader to understand technical spirit of the present invention and the beneficial effect that can produce better, can not be interpreted as any qualification to the scope of the present invention.
Embodiment 1: internal-circulation type jet-type resorber
See also Fig. 3 and shown in Figure 4, present embodiment provides a kind of simple and practical absorption reactor thermally.
This absorption reactor thermally 20 is made of nozzle 21 and reaction tubes 22, nozzle 21 is made up of interior pipe 211 and sleeve pipe 212, interior pipe 211 is a hollow tube substantially, the upper end is liquid inlet 2111, and the lower end is the liquid exit 2112 of convergent, manages outside 211 in sleeve pipe 212 is sheathed on, be sealing between top and outer wall of inner tube, the bottom then with extraneous conducting, have annular space 213 between sleeve pipe 212 and the interior pipe 211, and the sidewall appropriate location of sleeve pipe 212 is provided with gas inlet 2121 and communicates with annular space 213; As shown in Figure 4, the length of interior pipe 211 slightly is longer than sleeve pipe 212, and the liquid exit 2112 of lower end stretches out sleeve pipe 212 1 segment distances.
Be provided with the inner catheter 221 that two-port all communicates with reaction tubes in the reaction tubes 22 of this absorption reactor thermally 20, the two forms interlayer 222.Reaction tubes 22 tops and bottom are respectively equipped with first liquid discharge outlet 223 and second liquid discharge outlet, 224, the second liquid discharge outlets 224 form necking down; Inner catheter 221 is fixedly set in the reaction tubes 22, and between liquid discharge outlet 223 and 224, upper port 2211 forms the rim of a cup (uncovered) that an opening enlarges, and lower port remains with certain distance apart from reaction tubes 22 bottom necking downs.As shown in Figure 3, in the present embodiment, the expanding reach 226 that a sectional area increases is formed at the top of reaction tubes 22, can be beneficial to the circulation of absorption liquid, but the concrete shape and size of this expanding reach 226 does not have special requirement; Nozzle 21 is from the upper end insertion reaction pipe 22 of expanding reach 226, liquid exit 2112 just is positioned at rim of a cup 2211 tops of inner catheter 221, as shown in the figure, the rim of a cup of the upper port 2211 of inner catheter can be in reaction tubes 22 top expanding reach formation place, and with reaction tubes 22 conductings.The upper end appropriate location of expanding reach 226 also offers tail gas outlet 225.The upper end of expanding reach can be sealing in operation, and by nozzle and extraneous conducting, if desired, the reaction tubes sidewall also can be provided with the liquid level control flume, in order to the absorption liquid measure in the monitoring reaction tubes.
When adopting the absorption reactor thermally operation of present embodiment, absorption liquid adds from the liquid inlet 2111 of the interior pipe 211 of nozzle 21, spray into the inner catheter 221 of the reaction tubes 22 of reactor by the outlet 2112 of convergent, H 2 S-containing gas is fed from the gas inlet 2121 of nozzle 21, be absorbed liquid through annular space 213 and carry the inner catheter 221 that enters reaction tubes 22.Promptly, the gas that absorption liquid carries from annular space 213 when nozzle 21 sprays enters inner catheter 221 through inner catheter rim of a cup 2211 with jeting effect, it is interior descending when gas-to-liquid contact takes place along inner catheter 221, and be up in the expanding reach 226 from interlayer 222 and enter inner catheter 221 from rim of a cup 2211 once more, form internal recycle (indicating) as arrow among the figure.
Above-mentioned internal-circulation type sprays resorber and adopts absorption liquid to carry the method that gas enters reactor, the circulation that utilizes liquid to flow fully contacts gas-liquid and reacts, finish whole absorption process, utilize the absorption reactor thermally of this structure that gas-liquid two-phase is prolonged duration of contact, thereby effectively improve assimilated efficiency; Simultaneously, absorption reaction mainly is to take place in working cycle, and the sulphur of generation is precipitated out at any time, the phenomenon of sulfur granule plug nozzle can not occur.After reaction is finished, emit a large amount of mixed solutions that contains sulphur (treating regenerated liquid) from first liquid discharge outlet 223, isolate sulphur after, solution can be sent into electrolyzer regeneration for recycling.Reaction tubes bottom is the higher absorption liquid of a small amount of sulphur content in the reaction process, optionally emits from second liquid discharge outlet 224 at any time, separates and make with extra care, send the refining plant processing treatment to become the high purity sulphur after the isolated elemental sulfur merging.
Utilize this absorption reactor thermally that the specific absorption of hydrogen sulfide is reached more than 90%, and the sulfur purity that makes is also more than 99.8%.
Embodiment 2: adopt double-reactor technology of recovery sulphur and hydrogen simultaneously from hydrogen sulfide containing sour gas
Idiographic flow sees also Fig. 5, mainly is made up of absorption, separation and electrolytic regeneration three parts.Specifically describe as follows:
Hydrogen sulfide containing sour gas feeds absorption reactor thermally 20 after metering, and absorption liquid (contains Fe 3+Solution) also send into absorption reactor thermally 20 after metering, by controlling suitable liquid/gas volume ratio, make absorption liquid carry gas and enter absorption reactor thermally 20 with spray regime, oxidizing reaction takes place in reactor for the two makes hydrogen sulfide be absorbed to generate sulphur, and the Fe in the absorption liquid 3+Be reduced into Fe 2+(having at least part to be reduced), this absorption liquid becomes at this moment treats regenerated liquid, from absorption reactor thermally 20, discharge, enter and treat regenerated liquid storage tank 4A (by high-order control flume 41), treat that regenerated liquid enters filtration pump 5 initial gross separation sulphur from treating regenerated liquid storage tank 4A outlet, through two groups of strainer tubes 61 and 62 further filtering separation, sulphur enters refining plant 7, treats that regenerated liquid then sends in the high-order storage tank 8 of anolyte.The concrete structure of the absorption reactor thermally 20 that uses in this absorption oxidising process and reaction process are introduced in embodiment 1 in detail, no longer repeat.
The regenerated liquid for the treatment of in the high-order storage tank 8 of anolyte utilizes anode pump 31 to send into electrolyzer 30, the bipolar board-like electrolysis reactor of record among the CN of patent formerly 200420047897.5 that this electrolyzer 30 is the applicant, its concrete structure and principle of work see also the description of the drawings and specific embodiments part of this patent.In the electrolytic process, at anode Fe 2+Be oxidized to Fe 3+Make regeneration of absorption solution, then return absorption liquid storage tank 4B, recycle (during running for absorption reactor thermally, valve such as needs between absorption reactor thermally bottom and storage tank 4A can be opened, a small amount of higher absorption liquid of sulphur concentration enters the 4A storage tank, and the valve between absorption reactor thermally and storage tank 4B is closed); H in the electrolytic process +Passing ion-exchange membrane enters negative electrode and is reduced to H 2, isolate hydrogen through separation drum 33, catholyte then returns electrolyzer 30 (through negative electrode pump 32), it all is routine techniques that concrete electrolytic process and hydrogen are collected, such as among the figure sign, no longer carefully state.
What discharged absorption reactor thermally 20 bottoms is the higher absorption liquid of a small amount of sulphur content, can artificially control during running and send into storage tank 4A, also sends into electrolysis reactor behind the Separation and Recovery sulphur as anolyte.
With the valve open between absorption reactor thermally 20 and storage tank 4B, discharge absorption liquid during the shut-down discharging.Above-mentioned absorption oxidizing reaction and electrolytic reaction process can realize the continuous operation of whole flow process by the combination of absorption reactor thermally and electrolysis reactor.
When the inventive method is used for commercial run, can unite with the hydramine absorption technique, show as empty frame part 90 among Fig. 5, sour gas (sulfide hydrogen) from the refinery absorbs through hydramine absorption tower 91 earlier, enter regenerator column 92 after making the reaction of hydrogen sulfide and hydramine, hydramine after the regeneration is returned pump 93 by hydramine and sends hydramine absorption tower 91 back to, enrichment the sour gas of hydrogen sulfide then enter gas sweetening tower 94, enter absorption reactor thermally 20 after the purification, according to the description process recovery sulphur and the hydrogen of front.
Embodiment 3
Operating process such as embodiment 2 describe, and adjust the stink damp speed and the absorption liquid (FeCl that send in the absorption reactor thermally 20 3) flow, measure the hydrogen sulfide absorption rate under the different acceptance conditions.
1, sour gas (sulfide hydrogen) gas speed 40-100L/h, liquid phase flow 300-500L/h controls the liquid/gas volume ratio in the 3-10 scope, Fe in the absorption liquid 3+The about 0.6M of concentration, Fe in the absorption liquid 2+The about 0.6M of concentration, hydrogen ion concentration is about 8M (HCl system), and absorption reaction is a normal pressure, and temperature is 40 ℃.
Write down in the sour gas that enters absorption reactor thermally respectively and hydrogen sulfide content (the fixed liquid phase flow in the tail gas of discharge reactor, change the gas speed of sour gas), calculate the specific absorption (%) of hydrogen sulfide, obtain the curve of Fig. 6, as can be seen, absorption liquid all is higher than 99% basically to the specific absorption of hydrogen sulfide, illustrates that technology of the present invention has higher turndown ratio to the air input variation of hydrogen sulfide.
2, the liquid/gas that fixedly enters absorption reactor thermally changes Fe in the absorption liquid than (about 6) 3+Concentration, absorption liquid are the HCl system, and hydrogen ion concentration is 8M, and absorption reaction is a normal pressure, and temperature is 40 ℃.
Write down in the sour gas that enters absorption reactor thermally respectively and the hydrogen sulfide content in the tail gas of discharge reactor, calculate the specific absorption (%) of hydrogen sulfide, obtain the curve of Fig. 7.Experiment shows that assimilated efficiency just can obviously descend when ferric ion concentration is lower than 0.18mol/L, and when being higher than 0.18mol/L, the specific absorption of hydrogen sulfide is 100% basically.Illustrate that technology of the present invention also provides bigger adjustable leeway for the electrolysis reactor operation.
3, sour gas (sulfide hydrogen) gas speed 40-50L/h, liquid phase flow 300-500L/h controls the liquid/gas volume ratio in the 3-10 scope, Fe in the absorption liquid 3+The about 0.7M of concentration, Fe in the absorption liquid 2+The about 0.7M of concentration, hydrogen ion concentration is about 6M (HCl system), and absorption reaction is a normal pressure, and temperature is 70 ℃.Change the content of hydrogen sulfide in the sour gas, investigate absorption result when hydrogen sulfide content is respectively 2%, 10%, 50%, 95% (other gas is nitrogen) in the sour gas.
Experiment shows that absorption liquid all is higher than 90% basically to the specific absorption of hydrogen sulfide.Illustrate that technological design of the present invention is very wide in range for hydrogen sulfide content requirement in the handled sour gas, do not require also that for the lower sour gas of hydrogen sulfide content must carry out enrichment in advance handles; And, adopt technology of the present invention can realize the stink damp effective as selective is absorbed, can not influence the absorption effect of system with other gases of hydrogen sulfide coexistence.
Embodiment 4: absorb the system combined running experiment of oxidation-electrolytic hydrogen production
Technical process such as Fig. 5, and referring to the description of embodiment 1 and 2.Experiment parameter is:
Fig. 8 has shown the changing conditions of Fe (II) concentration in this operation process.Fig. 9 has shown the changing conditions (absorption liquid and catholyte are the HCl system) of HC l concentration in this operation process.Figure 10 has shown hydrogen sulfide absorption rate and absorption rate changing conditions in the reaction process.Figure 11 has shown the changing conditions of electrolytic hydrogen production speed and power consumption in the operation process.
From the result of Fig. 8-Figure 11 as can be seen, the present invention adopt double-reactor to unite to absorb and the process of hydrogen manufacturing after the fluctuation of having experienced the initial stage, the composition of absorption and electrolysis system tends towards stability.The H of while system in whole operation process +Keep balance, the acid in the explanation system does not consume in reaction process.Accumulative total is produced the about 102mol of hydrogen in the experimentation.
The hydrogen sulfide absorption rate of system is about 100% in the whole service process, the about 2.6kwh/Nm of hydrogen manufacturing power consumption 3H 2The sulphur that generates purity by analysis is more than 99%.
The result shows: two reactor system of the present invention can realize hydrogen sulfide desulfurization and hydrogen manufacturing steady running, and expanding test device hydrogen manufacturing amount reaches 80-100L/h, electrolytic hydrogen production power consumption≤2.6kwh/NM 3H 2, during hydrogen sulfide content in air inlet 〉=95% (V), the specific absorption of hydrogen sulfide is near 100%, the sulfur purity that is obtained>99%, and positive cathode efficiency is near 100% simultaneously.

Claims (10)

1, recovery sulphur and produce the method for hydrogen from H 2 S-containing gas, it comprises: adopt the absorption liquid that contains ferric ion in absorption reactor thermally hydrogen sulfide to be oxidized to sulphur, with wherein ferric ion is to send into electrolysis reactor as anolyte after absorption liquid that part is reduced to ferrous ion is isolated sulphur at least, recycle for absorption reactor thermally through electrolytic regeneration, produce hydrogen from the negative electrode of electrolysis reactor simultaneously; Wherein, the nozzle of control absorption liquid process absorption reactor thermally enters absorption reactor thermally and simultaneously H 2 S-containing gas is brought into, and control liquid/gas volume ratio is at 3-10.
2, method according to claim 1, wherein, absorption liquid is brought hydrogen sulfide containing gas into absorption reactor thermally simultaneously through nozzle, makes absorption liquid and gas contacts mixing in the reaction tubes of reactor and the gas-liquid mixture of formation is formed in reactor circulating.
3, method according to claim 1 and 2, wherein, described absorption liquid is an acid system, and ferric ion concentration is greater than 0.18 mol when entering absorption reactor thermally, and negatively charged ion is chlorion or sulfate ion, service temperature 20-80 ℃.
4, method according to claim 1 and 2, wherein, absorbing hydrogen sulphide gas and the process that generates sulphur adopt the absorption reactor thermally can make gas-liquid mixture realize internal recycle, the reaction tubes top of this absorption reactor thermally is provided with the nozzle of being made up of interior pipe and sleeve pipe, pipe upper end is the liquid inlet in it, the lower end is liquid exit and the reaction tubes import that is positioned at absorption reactor thermally top, casing pipe sleeve is located at outside the interior pipe, be sealing between top and outer wall of inner tube, the bottom then with extraneous conducting, form annular space between sleeve pipe and the interior pipe, and this sleeve pipe sidewall also is provided with the gas inlet that communicates with annular space;
During operation absorption liquid added from the liquid inlet of interior pipe and enter the reaction tubes of reactor, H 2 S-containing gas is fed from the gas inlet, be absorbed liquid through annular space and carry the reaction tubes that enters reactor by outlet.
5, method according to claim 4, wherein, the reaction tubes top of described absorption reactor thermally and bottom are respectively equipped with first liquid discharge outlet and second liquid discharge outlet, be arranged with the inner catheter that two-port all is conducted with reaction tubes in the described reaction tubes, and this inner catheter is arranged between two liquid discharge outlets of reaction tubes, and the liquid exit of nozzle just is positioned at inner catheter upper port top, the gas that absorption liquid is carried from annular space when nozzle sprays enters inner catheter, descending along inner catheter in gas-to-liquid contact, and, form internal recycle from the up upper port that enters inner catheter once more of the interlayer between reaction tubes and the inner catheter.
6, method according to claim 5, wherein, in the working cycle, the ferric ion of emitting wherein from first liquid discharge outlet on absorption reactor thermally top is the absorption liquid that part is reduced to ferrous ion at least, send into electrolysis reactor as anolyte behind the Separation and Recovery sulphur, through electrolytic oxidation is that the absorption liquid that contains ferric ion returns absorption reactor thermally, collects the hydrogen that discharges from negative electrode in the electrolytic process simultaneously.
7, according to claim 5 or 6 described methods, wherein, the ferric ion of emitting wherein from second liquid discharge outlet of absorption reactor thermally bottom is the absorption liquid that part is reduced to ferrous ion at least, send into electrolysis reactor as anolyte behind the Separation and Recovery sulphur, through electrolytic oxidation is that the absorption liquid that contains ferric ion returns absorption reactor thermally, collects the hydrogen that discharges from negative electrode in the electrolytic process simultaneously.
8, method according to claim 1, wherein, electrolytic process adopts bipolar board-like electrolysis reactor.
9, method according to claim 1, wherein, stink damp concentration is 2-100% in the described H 2 S-containing gas.
10, method according to claim 3, wherein, described absorption liquid consists of Fe 2+Concentration 0.3-0.7M, Fe 3+Concentration 0.3-0.8M, H +Concentration 2-10M.
CNB2006100580638A 2006-02-28 2006-02-28 Method for recovering sulfur and making hydrogen from hydrogen sulfide CN100450917C (en)

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