CN101227964A - Process for producing a gas stream depleted of hydrogen sulphide and of mercaptans - Google Patents

Process for producing a gas stream depleted of hydrogen sulphide and of mercaptans Download PDF

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Publication number
CN101227964A
CN101227964A CNA2006800267995A CN200680026799A CN101227964A CN 101227964 A CN101227964 A CN 101227964A CN A2006800267995 A CNA2006800267995 A CN A2006800267995A CN 200680026799 A CN200680026799 A CN 200680026799A CN 101227964 A CN101227964 A CN 101227964A
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gas stream
rsh
poor
cuso
feed gas
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T·拉斯特
A·卡尔松
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1487—Removing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention provides a process for producing a gas stream depleted of H2S and of RSH from a feed gas stream comprising H2S and RSH, the process comprising the steps of : (a) contacting the feed gas stream with absorbing liquid in a H2S removal zone to obtain a gas stream depleted of H2S; (b) contacting the gas stream obtained in step (a) with aqueous scrubbing solution comprising CUSO4 in a RSH removal zone to obtain a mixture comprising Cu-alkylsulphide products and the gas stream depleted of H2S and depleted of RSH.

Description

Produce the method for the gas stream of depleted of hydrogen sulphide and depleted of mercaptans
Technical field
The present invention relates to produce depleted of hydrogen sulphide (H 2S) and the method for the gas stream of depleted of mercaptans (RSH).
Background technology
Produce the poor H that contains 2The gas stream of S and the poor RSH of containing comprises and removes these compounds.Consider to continue strict environmental specification, remove H from the gas stream that comprises these compounds 2S and RSH are quite important always in the past and at present even especially like this.
Many natural gas wells produce " acid gas ", promptly comprise H with RSH usually 2The natural gas of S.The total amount of sulphur compound is too high usually, makes natural gas be unsuitable for direct use.Paid suitable effort to find to remove the measure that these do not wish the effective and cost economy of compound.In addition, natural gas can further comprise the carbon dioxide of variable quantity, according to the purposes of natural gas, must remove carbon dioxide to small part usually.
With remove H 2S compares usually that more difficult to remove RSH from gas stream be important, this be because mercaptan since their odor property can under a few millionths part concentration level, detect.Therefore, gas stream is intended for use to need to make under the situation of domestic use RSH concentration to drop to as less than 5 or even less than 2ppmv therein.
Gas stream is a carrier gas stream therein, inert gas or be used under the situation of appropriate hydrocarbon gas that stripping contains the reactor beds of RSH and load RSH for example, and it also is important that RSH removes.It is necessary can reuse gas stream as stripping gas removing RSH from the gas stream of this load.
Wherein to remove important another kind of situation be further to process the poor situation that contains the gas logistics to RSH.For example, natural gas can be used for typically producing forming gas in gasifier unit.Be converted into hydrocarbon known in the art for the forming gas that will form so usually in the catalysis process of Fischer-Tropsch process.If mercaptan exists in natural gas stream, they can reaction form H in gasifier 2S obtains comprising H 2The forming gas logistics of S.H 2S may be irreversibly combination and cause sulfur poisoning on catalyst.This causes seriously hindering the catalyst of the inactivation of catalytic process.Therefore method comprises under the situation of catalytic step therein, requires mercaptan is removed to be low to moderate less than 2ppmv or even low-down level in the scope of ppbv.
Usually, need be less than the sulphur compound total concentration of 30ppmv.The acid gas standard is mentioned less than 10ppmv usually or even is low to moderate total sulphur concentration less than 4ppmv.
From comprising H 2It is known in the art that the gas stream of S and RSH is produced the poor method that contains the gas stream of these two kinds of compounds.Usually, this known method is based on physics and/or chemical absorbing, solid bed adsorption and/or chemical reaction.But, have many shortcomings in the known method.Physical absorption process is subject to the following fact usually: need big reactor to reach required low RSH concentration.The solid bed adsorption method is subject to the following fact: they only can adsorb the limited amount compound of not wishing, and regeneration is to bother relatively, for example referring to US4, and 311,680.Big Solid Bed needs the more relatively recovery time and disproportionately needs a large amount of regeneration gas.Chemical method can remove H usually 2S, but they are subject to the following fact: and they can not remove RSH effectively and produce a large amount of refuses usually, for example referring to EP 229,587.
Comprise a large amount of relatively H in feed gas stream 2S and RSH and randomly have special problem under the situation of carbon dioxide.Purpose is to produce the poor H of containing from this feed gas stream 2The method of the gas stream of S and the poor RSH of containing is known in the art.
For example,, a kind of method has been described in 957,715, wherein by in first step, using adsorbent to remove H at US4 2S and a part of RSH carry out carrying out washing treatment subsequently removing carbon dioxide and other a part of RSH, and remove H from gas stream in second step 2RSH and carbon dioxide that S, alkyl replace.At US4, the shortcoming of the method for describing in 957,715 is a large amount of adsorbent of requirement, particularly when the amount of sulphur compound in the unstrpped gas is higher.
At US 5,700, described by logistics being contacted with copper compound and removing H in 438 from gas stream 2The method of S and RSH.But owing to need hindered amine-copper complex, this is a method expensive and effort.In addition, do not remove the carbon dioxide that exists in the feed gas stream.
At US5, a kind of method has been described in 424,051, wherein at first remove carbon dioxide and in second step, remove remaining carbon dioxide, H by alkaline washing by adsorbent 2S and RSH and remove carbon dioxide, H 2S and RSH.This method is expensive and effort and produces considerable used wash liquid refuse in addition.
At US4, described in 311,680 by using iron oxide fixed bed, remove H by reaction regeneration absorbent subsequently with hydrogen peroxide 2The method of S and RSH.This method needs a large amount of adsorbents, and regeneration simultaneously is expensive and effort.
At EP0, use CuSO has been described in 986,432 4The aqueous solution removes the method for amounts of sulphur contaminants.Although showed H 2S removes, but the removing of not mentioned RSH.Usually, RSH and H 2S compares and more is difficult to remove.In addition, at EP0, do not remove carbon dioxide in the method for describing in 986,432.
At US5, use CuNO has been described in 147,620 3The aqueous solution removes H 2The method of S.At US5, the shortcoming of the method for describing in 147,620 is to have formed NO 2This compound be corrosivity, toxicity and be environmental contaminants in addition.Therefore its formation is undesirable.
Consider the difficulty that in known method, runs into, need in this area particularly from comprising a large amount of relatively H 2The feed gas stream of S and RSH is produced the poor simple and universal method that contains these pollutants, and does not have the operational issue of known method and do not produce undesirable useless compound.
Summary of the invention
For this purpose, the invention provides from comprising H 2The feed gas stream of S and RSH is produced the poor H that contains 2S and the poor method that contains the gas stream of RSH, described method comprises the steps:
(a) at H 2S removes described feed gas stream is contacted with absorbing liquid, to obtain the poor H of containing 2The gas stream of S;
(b) remove the gas stream that makes acquisition in the step (a) in the district and comprise CuSO at RSH 4Wash water solution contact, to obtain to comprise the mixture and the poor H of containing of Cu-alkyl sulfur compounds product 2S and the poor gas stream that contains RSH.
The specific embodiment
Method of the present invention can be produced the poor H of containing 2S and the poor gas stream that contains RSH, wherein H 2The concentration of S be lower than suitably 10ppmv and wherein the concentration of RSH be lower than 10ppmv suitably.
In the step (a) of the inventive method, with H 2S transfers to from feed gas stream and absorbs liquid to obtain the poor H of containing 2The gas stream of S.
Can handle and comprise H 2Any feed gas stream of S and RSH.Suitably, feed gas stream comprises natural gas or associated gas, but also can handle other gas stream, for example the hydrogeneous refinery logistics that obtains after desulphurization reaction.Natural gas is the generic term that is used for from the natural gas well light hydrocarbon that obtains and the mixture of choosing other gas (nitrogen, carbon dioxide, helium) wantonly.The key component of natural gas is a methane.Usually there are ethane, propane and butane in addition.Can exist (lacking) amount to be typically expressed as the more higher hydrocarbon of natural gas liquids or condensate in some cases.When producing with oil, natural gas is commonly referred to associated gas.May comprise H with other compound that variable quantity exists in natural gas 2S, aliphatic series and/or aromatics RSH, sulfide, disulphide (carbon disulfide (CS particularly 2)), thiophene and carbon dioxide.
Method of the present invention is particularly suitable for removing H 2The feed gas stream that also comprises the significant quantity carbon dioxide beyond the S, this is owing to remove this two kinds of compounds effectively in the liquid absorption process in step (a).
The total raw material gas stream comprises the H of 0.05-20vol% suitably 2The RSH of S, 1ppmv to 1vol% and 0-40vol% carbon dioxide, the H of preferred 0.1-5vol% 2The RSH of S, 20ppmv to 1vol% and 0-30vol% carbon dioxide are based on total raw material gas stream meter.In particular embodiment of the present invention, the total raw material gas stream comprises the H of 0.15-1.0vol% 2S.
Even can handle and have and H 2S compares high relatively amount R SH, and typically RSH (being expressed as ppmv) is to H 2S (being expressed as vol%) ratio is higher, typically is at least 50, is preferably at least 100, and more preferably at least 200, still more preferably at least greater than 250 feed gas stream.Because this at high proportion, the gas stream that obtains in step (a) still has high relatively RSH content.Method of the present invention can remove these RSH and not have problem in the step (b).
Absorbing liquid is to remove H from feed gas stream 2Any liquid of S.Suitable absorption liquid is chemical solvent, physical solvent or its mixture.
Suitable chemical solvent is primary amine, secondary amine and/or tertiary amine, especially derived from amine, particularly MEA (MEA), diethanol amine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA) (DIPA) and methyl diethanolamine (MDEA) or its mixture of monoethanolamine.Preferred chemical solvent is secondary amine or tertiary amine, preferably derived from the amines of monoethanolamine, and more especially DIPA, DEA, MMEA (monomethyl-monoethanolamine), MDEA or DEMEA (diethyl-MEA), preferred DIPA or MDEA.It is believed that these chemical solvents and acid compound such as H 2Therefore the S reaction removes H from feed gas stream 2S.
Absorb liquid and also can comprise so-called activator compound.It is believed that adding activator compound in absorbing liquid system improves removing of acid compound.Suitable activator compound is piperazine, methylethanolamine or (2-amino-ethyl) monoethanolamine, particularly piperazine.
Preferably, absorb liquid and comprise MDEA and piperazine.
Suitable physical solvent is sulfolane (ring tetramethylene sulfone and derivative thereof), aliphatic acid amides, N-methyl pyrrolidone, N-alkylated pyrrolidones and the corresponding mixture of pyridine ketone, methyl alcohol, ethanol and polyethylene glycol dialkyl ether or the mixture of these materials of sending.Preferred physical solvent is a sulfolane.It is believed that H 2S absorbs in physical solvent and therefore removes from feed gas stream.The advantage that use comprises the absorption liquid of physical solvent is except removing H 2Beyond the S, also remove aromatic compounds from feed gas stream.The example of aromatic compounds is benzene, toluene and dimethylbenzene (being referred to as BTEX or BTX).Aromatic compounds be carcinogenic substance and therefore their discharging must be lower than certain level.Therefore need to reduce the concentration of aromatic compounds (particularly BTX compound) in the gas stream.But the advantage of the inventive method is that the existence of aromatic compounds does not hinder removing of the middle RSH of step (b).Even can the pack processing aromatic-containing compound such as the feed gas stream of BTX therefore.
Absorption liquid in the step (a) also can be the mixed system that comprises chemical liquid and physics liquid.The special absorption liquid that preferably comprises chemical solvent and physical solvent, this is because their show good absorbability and for H with respect to suitable cost of investment and running cost 2The good selectivity of S.In addition, comprise in feed gas stream under the situation of carbon dioxide, also can in blended absorbent liquid, remove carbon dioxide, obtain the poor H of containing to bigger degree 2S and poor carbonated gas stream.Another advantage of mixed system is that they show under high pressure better, and performance is better under the pressure of 20-90bara especially.Therefore under situation,, then do not need depressurization steps if for example feed gas stream is the natural gas stream that under high pressure obtains with the feed gas stream pressurization.Another advantage is to use the proven physical/chemical absorption liquid of mixing rather than only uses moisture chemical absorbing liquid also to obtain the possibility of any carbon dioxide of flash distillation under relatively high pressure power (being 5-15bara).This has reduced as being used for reflooded recompression requirement.
The preferred liquid system that absorbs comprises water, sulfolane and secondary amine or tertiary amine, preferably derived from the amines of monoethanolamine, and more especially DIPA, DEA, MMEA (monomethyl-monoethanolamine), MDEA or DEMEA (diethyl-MEA), preferred DIPA or MDEA.The amount of water is preferably the 20-45 weight portion, and the amount that the amount of sulfolane is preferably 20-35 weight portion and amine is preferably the 40-55 weight portion, and the amount of water, sulfolane and amine is 100 weight portions together.Preferred range in most of the cases obtains optimum carbon dioxide eliminating.
Another kind of preferred water that liquid comprises 15-45 weight portion (preferred 15-40 weight portion), 15-40 weight portion sulfolane, the 30-60 weight portion of absorbing is derived from the secondary amine of monoethanolamine or the activator compound (preferred piperazine) of tertiary amine and 0-15wt% (preferred 0.5-10wt%), and water, sulfolane, amine and the activator amount together that all weight portions are taken into account adding based on total solution is 100 weight portions.This preferred absorption liquid body can remove these compounds from the gas stream that comprises carbon dioxide, hydrogen sulfide and/or COS.This provides advantage with respect to other method that can not remove carbon dioxide.When comparing with the same absorbent liquid that does not add primary amine or secondary amine compound, particularly secondary amine compound, obtain one or more following advantages: absorption rate of carbon dioxide is faster, load capacity is higher, the solvent/gas ratio is lower, the littler and reactivation heat requirement lower (obtaining littler cooling capacity) of Design of device.When comparing with the absorption liquid that comprises aqueous amine, particularly DMEA and piperazine, the adding of sulfolane can be produced the gas stream that comprises carbon dioxide of the pressure with middle pressure such as 3-15bara, preferred 5-10bara.
Advantage of the present invention be can regulating step (a) can produce the gas stream of depleted of hydrogen sulphide and the poor RSH of containing from the feed gas stream that further comprises other compound, particularly is selected from other compound of carbon dioxide, aromatic compounds and other amounts of sulphur contaminants.This method provides whether remove hydrogen sulfide and RSH compound in addition, for example selection of other sulfur-containing compound or carbon dioxide or aromatic compounds from feed gas stream.Therefore, can pass through to absorb in the regulating step (a) selection of liquid suitably, reach the gas streams that in step (a), obtain different compositions.
Suitably, step (a) is carried out under 15-90 ℃ temperature, preferably at least 20 ℃, more preferably 25-80 ℃, still more preferably carry out and even still more preferably under about 55 ℃, carry out under 40-65 ℃ the temperature.Step (a) is suitably at 10-150 crust, carry out under the pressure of 25-90bara especially.
Step (a) is carried out in the zone of containing 5-80 contact layer such as valve plate, bubble cap plate, baffle plate etc. suitably.Also can use structured packing.Can be by regulating solvent/feed gas ratio optimization CO 2-the degree that removes.Suitable solvent/feed gas ratio is 1.0-10 (w/w), preferred 2-6.
The poor H that contains of gas stream that in step (a), obtains 2S means the H in the gas stream that obtains in step (a) 2S concentration is less than the H in the feed gas stream 2S concentration.H in the gas stream that understanding obtains in step (a) 2S concentration depends on the H in the feed gas stream 2S concentration.Typically, the H in the gas stream that in step (a), obtains 2S concentration is H in the feed gas stream 2The 80-0.0001% of S concentration, preferred 20-0.001%, more preferably 10-0.0001%.Suitably, the H in the gas stream that in step (a), obtains 2S concentration is less than 10ppmv, preferably less than 5ppmv.
Should understand the poor H of containing that obtains afterwards in step (a) 2RSH concentration in the gas stream of S depends on the RSH concentration in the feed gas stream.Suitably, the poor H that contains that obtains afterwards in step (a) 2RSH concentration in the gas stream of S is 100ppbv to 0.1vol%.
In step (a), obtain to comprise H 2S and optional CO 2And/or C 3The absorption liquid of the load of+RSH and other sulphur compound (as carbonyl sulfide).Step (a) is carried out as continuation method usually, and this method also comprises the regeneration of the absorption liquid of load.Therefore, H 2S removes the district and preferably further comprises at least one regenerator, in this regenerator typically under low relatively pressure and high temperature by making at least a portion pollutant transfer to the regenerate absorption liquid of load of regeneration gas stream.The absorption liquid of load removes H 2S and optional CO 2And/or comprise beyond the COS obvious amount from other compound of the admixture of gas of wanting purifying such as hydrocarbon, carbon monoxide, hydrogen etc.Can advantageously belong to CO by being flashed to be higher than 2With optional H 2The pressure of the dividing potential drop summation of S and/or COS and these (non-acid) compounds being removed at least in part from the solvent of load.Adopt this mode only to discharge the very CO of smallest number from solvent with (non-acid) compound 2With optional H 2S and COS.Can be advantageously the absorption liquid of load be flashed in second step and be lower than CO under main temperature 2With optional H 2The pressure of the dividing potential drop of S and/or COS promptly is flashed to the pressure of common 1-5bara.Usually flash distillation is at the pressure of 1-15bara, preferred 1-10bara, more preferably carry out under the environmental pressure.Preferably under atmospheric pressure carry out flash distillation.There are a large amount of carbon dioxide and optional H in the gas that during flash distillation, discharges 2S and/or COS.Temperature in the last flash distillation operation is 50-120 ℃, preferred 60-90 ℃ suitably.
Preferably, the absorption liquid of the load that randomly regeneration obtains in step (a) after above-mentioned flash distillation.By heating and regenerating suitably under 70-150 ℃ relatively-high temperature degree suitably in regenerator.Preferred steam or the deep fat of adopting heats.Preferably, progressively increase temperature.Suitably, regeneration is carried out under the pressure of 1-2bara.
After regeneration, the absorption liquid of acquisition regeneration and load pollutant such as hydrogen sulfide, C 3The regeneration gas stream of the load of+RSH and/or optional carbon dioxide and carbonyl sulfide.Preferably, the absorption liquid with regeneration is used for H once more in the absorption stage of step (a) 2S removes.Suitably, with the absorption liquid of regeneration and the absorption liquid heat exchange of load to use described heat elsewhere.Suitably, in sulfur recovery unit, for example remove sulphur compound from the regeneration gas stream of load by the Claus method.
In the step (b) of the inventive method, remove in the district by making the poor H of containing that obtains in the step (a) at RSH 2The gas stream of S with comprise CuSO 4Wash water solution contact and the gas stream that obtains from step (a) removes RSH, therefore acquisition comprises the mixture and the poor H of containing of Cu-sulfide product 2S and the poor gas stream that contains RSH.
RSH refers to referred in this: aliphatic RSH, particularly C 1-C 6RSH, more especially C 1-C 4RSH; Aromatics RSH, particularly phenyl mercaptan; Or the mixture of aliphatic series and aromatics RSH.The present invention be more particularly directed to remove methyl RSH (it is considered to by one of the most difficult RSH that removes of conventional liq absorption techniques), ethanethio, n-pro-pyl and isopropyl mercaptan and butyl mercaptan isomers.
It is believed that RSH and CuSO in step (b) 4Reaction mainly be following reaction, but be not limited thereto:
2 RSH+CuSO 4→R-S-Cu-S-R+H 2SO 4 (1)
If any H 2S still exists in gas stream, it is believed that at least a portion H 2S is converted into CuS according to following reaction equation:
H 2S+CuSO 4→CuS+H 2SO 4 (2)
Cu-sulfide product refers to and comprises the single sulfide of Cu-or Cu-di-sulphide compounds or both, typically comprises the product of R-S-Cu-S-R and optional CuS referred in this.
Select the CuSO in the wash water solution 4The CuSO of the feasible dissolving of concentration q.s 4, but CuSO does not take place 4Precipitation or CuSO 4Precipitation less.Preferably, the CuSO in the wash water solution in the step (b) 4Concentration is that 0.1wt% is extremely saturated, and preferred 1wt% is to saturated, based on total wash solution meter.Randomly, wash water solution further comprises acid compound, preferred H 2SO 4
Suitably, step (a) and step (b) are carried out in the gas/liquid contactor.Suitable gas/liquid contactor for example is described in Perry ' s Chemical Engineers ' s Handbook, and the 7th edition, the 14th saves (1997) and comprise injector.
In step (b), the gas stream that obtains in the step (a) preferably spurted into and comprise CuSO 4Wash water solution in.This guarantees the optimum contact between gas stream and wash solution.
Preferably, method of the present invention comprises that the mixture that obtains separates the other step (step (c)) of at least a portion Cu-sulfide product from step (b).This for example can be by filtering or preferably reaching by the density separation step.Randomly, at least a portion Cu-sulfide product that removes like this can be converted into CuO according to following reaction equation then:
x R-S-Cu-S-R+y O 2→x CuO+2x SO 2+z CO 2 (3a)
2cCuS+3O 2→2CuO+2SO 2 (3b)
The preferred operations temperature of roast area is greater than 150 ℃.Preferably, the operating pressure of roast area is 1-5bara.
Suitably, then can be at CuSO 4At least a portion CuO that will form like this in the renewing zone is converted into CuSO according to following reaction equation 4:
CuO+H 2SO 4→CuSO 4+H 2O (4)
Suitably, at CuSO 4Environment for use temperature and pressure in the renewing zone.
Preferably, the CuSO that at least a portion is formed from CuO 4Directing into RSH removes the district and is used for step (b).Randomly, from CuSO 4Renewing zone evaporation and remove excessive H 2O.
As substituting of roasting, the Cu-sulfide that at least a portion is formed removes and for example delivers to the copper melting device and remove the new CuSO of adding in the district to RSH from process 4
Method of the present invention can adopt continuous mode to carry out, preferred cyclic regeneration process and the CuSO that absorbs liquid that use 4The cyclic regeneration process carry out.
Can adopt the poor H of containing that obtains in the further in a known manner treatment step (b) 2S and the poor gas stream that contains RSH.For example, gas stream can be experienced catalysis or noncatalytic combustion with generating, heat or power, maybe can be as the unstrpped gas of chemical reaction or domestic use.Comprise in feed gas stream under the situation of natural gas, also the gas stream that obtains in the step (b) can be converted into liquefied natural gas (LNG).
The present invention is now by following non-limiting example explanation.
Embodiment 1 (contrast)
Under the pressure of 45 ℃ temperature and 60barg, contact in absorber unit forming feed gas stream and the absorption liquid that comprises sulfolane, MDEA and water shown in the A row of table 1.The composition that leaves the gas stream of absorber unit sees Table 1 B row.
Embodiment 2 (contrast)
Under the pressure of 45 ℃ temperature and 60barg, contact in absorber unit forming feed gas stream and the absorption liquid that comprises MDEA and piperazine shown in the A row of table 1.The composition that leaves the gas stream of absorber unit sees Table 1 C row.
Embodiment 3 (the present invention)
Under the pressure of 45 ℃ temperature and 60barg, contact in absorber unit forming feed gas stream and the absorption liquid that comprises sulfolane, MDEA and water shown in the A row of table 1.The composition that leaves the gas stream of absorber unit sees Table 1 B row.The gas stream that leaves absorber unit spurted in water, comprise 10wt% (based on total solution meter) CuSO 4Solution in.Use the CuSO that leaves of gas chromatographic measurement 4RSH concentration in the gas stream of solution is less than 2ppmv.
Embodiment 4 (the present invention)
Feed gas stream and the absorption liquid that comprises sulfolane, MDEA and water formed shown in the A row of table 1 are contacted under the pressure of 45 ℃ temperature and 60barg.The composition that leaves the gas stream of absorber unit sees Table 1 B row.The gas stream that leaves absorber unit spurted in water, comprise 10wt% (based on total solution meter) CuSO 4And 10wt% (based on total solution meter) H 2SO 4Solution.Use the CuSO that leaves of gas chromatographic measurement 4RSH concentration in the gas stream of solution is less than 2ppmv.
Table 1: in the concentration of component of mol%.All BTX and all RSH in ppmv.
A B C
H 2O 0.010 0.223 0.201
CO 2 2.118 0.002 0.000
H 2S 0.432 0.000 0.000
CH 3SH 0.004 0.000 0.003
C 2H 5SH 0.011 0.001 0.001
i-C 3H 7SH 0.001 0.000 0.001
N 2 3.715 3.831 3.811
C 1 84.622 86.814 86.715
C 2 5.387 5.499 5.529
C 3 1.777 1.798 1.823
iC 4 0.619 0.622 0.634
nC 4 0.654 0.652 0.670
iC 5 0.184 0.182 0.189
nC 5 0.159 0.156 0.163
C 6 0.135 0.129 0.138
C 7 0.058 0.053 0.058
C 8 0.019 0.017 0.019
Benzene 0.042 0.011 0.029
Toluene 0.019 0.005 0.015
All BTX (ppmv) 610 151 439
All RSH (ppmv) 165 12 73
Be apparent that from embodiment method of the present invention can produce RSH concentration less than 2ppmv and H 2Poor contain RSH and poor the contain H of S concentration in the ppbv scope 2The gas stream of S.Control methods obtains the gas stream of RSH concentration greater than 10ppmv.

Claims (12)

1. from comprising H 2The feed gas stream of S and RSH is produced the poor H that contains 2S and the poor method that contains the gas stream of RSH, described method comprises the steps:
(a) at H 2S removes described feed gas stream is contacted with absorbing liquid, to obtain the poor H of containing 2The gas stream of S;
(b) remove the gas stream that makes acquisition in the step (a) in the district and comprise CuSO at RSH 4Wash water solution contact, to obtain to comprise the mixture and the poor H of containing of Cu-alkyl sulfur compounds product 2S and the poor gas stream that contains RSH.
2. the method for claim 1 further comprises the steps:
(c) remove differentiation from least a portion Cu-sulfide product from described RSH.
3. the method for claim 2 further comprises the steps:
(d) in roast area, at least a portion Cu-sulfide product that separates in the step (c) is converted into CuO;
(e) at CuSO 4In the renewing zone at least a portion CuO product that obtains in the step (d) is converted into CuSO 4
4. each method of claim 1-3, wherein the described absorption liquid in the step (a) comprises chemical solvent and physical solvent.
5. each method of claim 1-4, wherein the described absorption liquid in the step (a) further comprises water.
6. each method of claim 1-5, the wherein CuSO of new wash water solution in the step (b) 4Concentration is that 0.1wt% is extremely saturated, and preferred 1wt% is to saturated, based on all wash solution meters.
7. each method of claim 1-6, wherein said wash water solution further comprises H 2SO 4
8. each method of claim 1-7 is wherein by spurting into gas the described CuSO of comprising 4Wash water solution carry out step (b).
9. each method of claim 1-8, wherein said feed gas stream comprises natural gas.
10. each method of claim 1-9, the concentration of RSH is 1ppmv to 1vol% in the wherein said feed gas stream, based on the feed gas stream meter.
11. each method of claim 1-10, wherein the described absorption liquid in the step (a) comprises one or more solvents that are selected from MEA (MEA), diethanol amine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA) (DIPA) and methyl diethanolamine (MDEA).
12. each method of claim 1-11, wherein the described absorption liquid in the step (a) comprises and is selected from sulfolane, aliphatic acid amides, N-methyl pyrrolidone, N-alkylated pyrrolidones and corresponding one or more compounds of sending pyridine ketone, methyl alcohol, ethanol and polyethylene glycol dialkyl ether.
CNA2006800267995A 2005-07-22 2006-07-13 Process for producing a gas stream depleted of hydrogen sulphide and of mercaptans Pending CN101227964A (en)

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