CN107866132A - SO in one kind processing Claus tail gas2Absorbing liquid and processing method - Google Patents
SO in one kind processing Claus tail gas2Absorbing liquid and processing method Download PDFInfo
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- CN107866132A CN107866132A CN201610855781.1A CN201610855781A CN107866132A CN 107866132 A CN107866132 A CN 107866132A CN 201610855781 A CN201610855781 A CN 201610855781A CN 107866132 A CN107866132 A CN 107866132A
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- absorbing liquid
- tail gas
- amine
- gas
- claus tail
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- 239000007788 liquid Substances 0.000 title claims abstract description 82
- 238000012545 processing Methods 0.000 title claims abstract description 10
- 238000003672 processing method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 46
- 150000001412 amines Chemical class 0.000 claims abstract description 36
- 238000011069 regeneration method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008929 regeneration Effects 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 238000000746 purification Methods 0.000 claims description 22
- 150000004985 diamines Chemical class 0.000 claims description 13
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical group CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 7
- 229940043276 diisopropanolamine Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 20
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 95
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005504 petroleum refining Methods 0.000 description 4
- -1 Amido isopropanol Chemical compound 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000032696 parturition Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 101100258301 Arabidopsis thaliana SUV3 gene Proteins 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- WGIAYBNWTYECJD-UHFFFAOYSA-N 1-ethoxypiperazine Chemical compound CCON1CCNCC1 WGIAYBNWTYECJD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101000604197 Homo sapiens Neuronatin Proteins 0.000 description 1
- 101000999322 Homo sapiens Putative insulin-like growth factor 2 antisense gene protein Proteins 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 102100038816 Neuronatin Human genes 0.000 description 1
- 102100036485 Putative insulin-like growth factor 2 antisense gene protein Human genes 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- 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
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/2041—Diamines
Landscapes
- 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)
- Treating Waste Gases (AREA)
Abstract
The invention discloses one kind to handle SO in Claus tail gas2Absorbing liquid and its processing method, SO is removed from process gas by the absorbing liquid and processing method2, rich in SO2Absorbing liquid by steam stripping regeneration system reusable edible, purpose of the present invention is reached with this.Described absorbing liquid has the characteristics that：（1）Contain one or more reproducible organic amines in absorbing liquid；（2）Contain one or more organic amine activating agents in absorbing liquid；（3）Contain one or more organic amine reaction promoters in absorbing liquid；（4）Contain 50 ~ 88% in absorbing liquid（wt）Water.The invention also discloses SO in a set of processing Claus tail gas2Flow and device, SO can be realized by the absorbing liquid and device2Volume content is from 300 ~ 60000 mg/m3Purify to 20 mg/m3Hereinafter, the SO desorbed2Byproduct concentration is more than 99.5%.
Description
Technical field
The invention belongs to the technical fields such as gas separation, gas purification, air environmental protection, and in particular to one kind processing Claus
SO in tail gas2Absorbing liquid and method.The invention further relates to a kind of equipment for realizing this method, the equipment is included by absorbing
Tower, regenerator, heat exchanger, boiling device, regeneration gas separating device, circulating pump form a set of to SO2The dress absorbed, regenerated
Put, to realize recycling for absorbing liquid.
Background technology
In the industrial process such as petroleum refining and process, natural gas extraction, coal gasification preparing synthetic gas, generally produce big
Amount is with hydrogen sulfide（H2S）For carbon-based sulphur of advocating peace（COS）, sulfur-bearing industrial waste gas supplemented by the organic sulfur such as mercaptan.These sulphur-containing exhaust gas
In sulfide toxicity it is big, should not directly discharge, generally burn after with SO2Form be discharged into air.Developed country is to industrial mistake
SO in journey2Discharge limitation, total trend is more and more severe.In the existing national atmosphere pollutants emission standardses system in China
In, generality discharge performs GB16279-1996《Discharge standard of air pollutants》, special industry such as petroleum refining industry
Perform《Petroleum refining industry pollutant emission standard》（Exposure draft）, thermal power plant perform GB13223-1996《Thermal power plant is big
Gas pollutant emission standard》Deng.That puts into effect or revise recently from China multiple is related to SO2Knowable to the standard of discharge, industrial waste gas
Middle SO2Emission concentration standard will be more and more lower, wherein GB13223-2011《Fossil-fuel power plant atmospheric pollutant emission standard》Counterweight
The SO in point area2Concentration of emission has required to be less than 50mg/m3,《Petroleum refining industry pollutant emission standard》（Exposure draft）
Key area is also required to be less than 100mg/m3。
Claus tail gas is the most typical industrial sulphur-containing exhaust gas of the manufacturing enterprises such as petrochemical industry, natural gas purification, coal chemical industry,
And the SO of these production units discharge2One of important sources.In order to reduce the SO in discharge waste gas2Content, it is industrial frequent
Using catalysis Reducing and absorption（SCOT methods）, using Catalytic Hydrogenation Techniques by the SO in Claus tail gases2, COS and CS2Deng hydrogenation or
Hydrolysis is changed into H2S, again return in claus reaction device and utilize.But the investment of SCOT subtraction units is big, running cost is high, energy consumption
It is high, turn into SO in long-standing problem Claus tail gas2The bottleneck for the treatment of technology, it is difficult to break through.Moreover, with national environmental protection
The increasingly raising of standard, discharge flue gas can not much meet new environmental protection standard caused by existing Claus sulfur recovery technology
It is required that the technological innovation replacement is imperative.Therefore, research and development other technologies turn into study hotspot.In Claus process tail gas
SO2Removing can also use for reference SO in coal-fired flue-gas2Removing process.
The content of the invention
The purpose of the present invention is to be directed to SCOT subtraction units in Claus vent gas treatments to invest big, running cost height, and energy consumption occupies high
The problems such as not descending, and SO in a kind of Claus tail gas proposed2Absorbing liquid and processing method.
The main technical schemes of the present invention：Contain SO in Claus tail gas2Process gas by described flow and device with
Described SO2Absorbing liquid counter current contacting, absorbing and removing SO therein2, absorbing liquid passes through reusable edible after regeneration.
Absorbing liquid of the present invention includes 10 ~ 50%（wt）Organic diamine, 1 ~ 5%（wt）Organic amine activating agent, 2
~10%（wt）Organic amine reaction promoter and 50 ~ 85%（wt）Water.
The feature of the absorbing liquid provided is：（1）Contain one or more reproducible organic amines in absorbing liquid；（2）Inhale
Receive in liquid and contain one or more organic amine activating agents；（3）Contain one or more reaction promoters in absorbing liquid；（4）Absorbing liquid
SO in absorbing Claus tail gas under the conditions of 20 ~ 70 DEG C of low temperature, 0.1 ~ 0.5MPa of pressure2, in 90 ~ 130 DEG C of higher temperatures, pressure
By absorbing liquid steam stripping regeneration under the conditions of 0.1 ~ 0.4MPa；（5）It can be realized and recycled by the absorbing liquid after steam stripping regeneration.
SO of the present invention2In absorbing liquid, suitable total amine concentration range is 12 ~ 60%（wt）, but preferential concentration range
For 20 ~ 45% (wt).
SO of the present invention2Absorbing liquid, it is 35 ~ 50 DEG C to absorb temperature range, and regeneration temperature range is 100 ~ 115 DEG C.
Organic diamine of the present invention is renewable formula organic amine, for one or more organic diamines, including ring
Shape diamines etc., and in organic diamine two amine groups alkalescence it is different.
Organic amine activating agent of the present invention be hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, boric acid or citric acid in one kind or
It is a variety of.
Organic amine reaction promoter of the present invention is diisopropanolamine (DIPA)（DIPA）, isopropylamine base ethanol（IPAE）, isopropyl
Amido isopropanol（IPAIP）, isobutyl amine ethanol（IBAE）, isobutyl amine propyl alcohol（IBAP）, isobutyl amine isopropanol
（IBAIP）, tert-butylamine base propyl alcohol（TBAP）, tert-butylamine base isopropanol（TBAIP）, polyethylene glycol 400（PEG400）, ethoxy piperazine
Piperazine（HEPZ）, polyethylene glycol（PEG400）, morpholine（MOR）In one or more.
One or more organic amine activating agents of the present invention, in SO2Absorbing liquid does not absorb SO2Before with it is organic
The stronger amine groups of alkalescence in diamine react, generate it is stable, be difficult to the ammonium salt that regenerates；And another is alkaline
Weaker amine groups, the SO in Claus tail gas is not only absorbed then with organic amine active agent response, the group2, and be SO2Absorbing liquid
Adsorption equilibrium and power of regeneration, regenerating easily after heating are provided.
Described organic diamine contains 2 different amine groups of dissociation capability, has advantage on regeneration of absorption solution.Two
First amine is to SO2There are good absorbent properties, in aqueous itself and SO2The process of reaction and regeneration is as follows：
First, first basic group of diamine and SO2Reaction：
（1）
Such as formula（1）Salt that is shown, being formed with the stronger amido of alkalescence, stable performance, SO2It is not easy to desorb.
Described absorbing liquid, good regenerability is provided simultaneously with, because the quality of regenerability is directly connected to absorption
The re-absorption ability of agent, i.e. formula（2）Back reaction it is most important.
Diamine ion after first basic group reaction saturation continues to participate in reaction：
（2）
This process is reversible process, can inversely be carried out in the case where running into high-temperature condition, produces SO2Regeneration gas, and two after regenerating
First amine aqueous solution can go successively to absorption tower and reuptake SO2, to realize recycling for absorbing liquid.
Organic amine reaction promoter of the present invention, after diamine complex role, contains SO at the same time2And CO2Deng gas
Under the conditions of component, preference absorbs SO2。
SO involved in the present invention2In absorbing liquid, such as corrosion inhibiter, defoamer and similar components activating agent can also be included.
The concentration range of these activating agents is 0.01% ~ 2.5%（wt）, the use of these activating agents is well known to those skilled in the art
's.
Between 3 ~ 10, pH value can control between 5 ~ 7 the pH value of absorbing liquid of the present invention.
The invention further relates to one kind to handle SO in Claus tail gas2Method, this method and described organic amine absorbing liquid one
Rise and form overall technology, to realize the purpose of the present invention.
Further, SO in described processing Claus tail gas2Method, disclose SO in a set of processing Claus tail gas2's
Flow and device.
Described flow comprises the following steps：
1）Claus tail gases initially enter tail gas burning furnace, and air is blasted by blower fan, at high temperature that the sulphur of various forms is complete
Portion is converted into SO2；
2）Contain SO2The cooling of tail gas after incineration recovered waste heat after enter absorption tower, with organic amine absorbing liquid counter current contacting, tail
SO in gas2Absorbed by organic amine absorbing liquid, the tail gas after purification directly passes through smoke stack emission；
3）Rich in SO2Absorbing liquid enter regenerator, the poor amine liquid after steam stripping regeneration through heat exchange cool down after go back to absorption tower again
Recycle；
4）SO in regeneration gas2It can reach more than 99.5%（Butt, volume ratio）, high concentration SO2Regeneration gas is re-fed into Crouse
Device participates in reaction production sulphur.
In technology provided by the invention, described device includes tail gas burning furnace, air blower, absorption tower, regenerator, changed
The known common apparatus and tower such as hot device, boiling device, regeneration gas separating device, circulating pump；Formed in a set of tail gas to Claus
SO2The generalized flowsheet and equipment absorbed, regenerated.The equipment is atmospheric pressure device, and number of devices is few, investment reduction.
SO in absorbing liquid and method processing Claus tail gas of the present invention2Concentration is 300 ~ 60000 mg/m3, desulfurization
Afterwards, SO in emission2Concentration can reach 20 mg/m3Hereinafter, the SO desorbed2Byproduct concentration is more than 99.5%.
SO in Claus tail gas of the present invention2Absorbing liquid and its method compared with the handling process of SCOT methods, have
Advantages below：
1）Absorbing liquid absorbability is big, and energy consumption is low, and stability is good, does not produce solid waste, small to corrosion of equipment；
2）The absorption selectivity of absorbing liquid is good, and 90% above is SO in return gas2, it is substantially free of CO2, avoid and be not involved in reacting
Indifferent gas incorporation cause claus reaction stove deviate operation operating mode the problem of；
3）Device realizes recycling for absorbing liquid, operating process non-wastewater discharge；And produced in SCOT tail gas treatment process
Acid water need increase sour water processing unit；
4）Device therefor is atmospheric pressure device, and number of devices is few, and process simplification is easily operated, investment reduction；
5）Normal temperature and pressure source of the gas can be handled, compared with SCOT method techniques, temperature and pressure is raised before reducing gas hydrogenation
Energy consumption.
Brief description of the drawings
Fig. 1 is the simplification of flowsheet of the embodiment of the present invention.
In figure, 1- tail gas burning furnaces；2- tail gas burning furnace boilers；3- absorption towers；4- regenerators；5- boiling devices；6th, 8- is cold
But device；7- poor rich liquid heat exchangers；9- regenerates gas separating device；10- burns stove air blast；11st, 12- relay pumps.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not limited to following embodiments.The front and rear objective is not being departed from
Scope under, change be included in the present invention technical scope in.
Embodiment is to remove SO in Claus tail gas according to amine process of the present invention2Typical technique：
Claus tail gases initially enter tail gas burning furnace, and air is blasted by blower fan, at high temperature that the sulphur of various forms is whole
It is converted into SO2, contain SO2The cooling of tail gas after incineration recovered waste heat after enter absorb the bottom of the tower, and from absorption tower top spray
Organic amine absorbing liquid counter current contacting under and, the SO in tail gas2Absorbed by organic amine, the tail gas after purification can directly pass through chimney
Discharge.
Absorption tower is equipped with suitable column plate or filler, and the typical operation temperature in absorption tower is about at 20 ~ 70 DEG C, and pressure is about
In 0.1 ~ 0.5MPa.
Rich in SO2Absorbing liquid enter regenerator by heat exchange recovery heat, poor amine liquid after steam stripping regeneration exchanges heat
Absorption tower is gone back to after cooling again to recycle, high concentration SO2Regeneration gas is re-fed into Cross unit and participates in reaction production sulphur.
Regenerator is equipped with suitable column plate or filler, and for the typical operation temperature of regenerator about at 90 ~ 130 DEG C, pressure is big
About in 0.1 ~ 0.4MPa.
Embodiment
Direct measurement is carried out to the operating characteristics of specific absorbing liquid and its method on an experimental rig.The absorption of experiment
Tower internal diameter 50mm, the built-in porcelain Raschig rings of Φ 6 × 6 × 1, regenerator internal diameter 70mm, the built-in porcelain Raschig rings of Φ 8 × 8 × 1, regenerator
Bottom is equipped with boiling device.
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2
3.10%、H2O 32.50%, N261.1%（It is volume ratio）.
After the completion of the configuration of organic amine absorbing liquid major constituent, the concentrated sulfuric acid 2% is successively added, then add boric acid by absorbing liquid pH value
6 or so are tuned into, remaining is deionized water.
The absorbing liquid counter current contacting that unstripped gas enters from absorb the bottom of the tower and absorption tower jacking, the acid gas in gas are absorbed,
Purified gas is vented after entering the drop of gas-liquid separator recovery entrained with after being come out from tower top.
The rich solution of acid gas is absorbed to lead at the top of regenerator from absorption tower bottom, in regenerator with the steam counter-flow of rising
Contact and regenerated.Lean solution after regeneration is sent into absorption tower jacking row cyclic absorption after cooling.Come out from regeneration overhead
Gas enters regeneration Gas Cooler and reclaims the water vapour in gas, and regeneration gas collection after separation is handled.
Certain in gas flow, operating characteristics and the contrast of certain Gas Purification Factory operating characteristics of different absorbing liquid compositions are shown in
Table one.
Embodiment 1
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes 15%（wt）EDA, 5%（wt）DIPA, 2%（wt）'s
Dense H2SO4, add boric acid and absorbing liquid pH value be tuned into 6 or so, remaining is deionized water.Taken off according to the invention described above amine process
Except SO in Claus tail gas2Typical technique handled.The operation temperature on absorption tower is：20 DEG C, pressure is：0.1MPa；Again
Giving birth to tower operation temperature is：90 DEG C, pressure is：0.1MPa.Effect is shown in Table one after purification.
Embodiment 2
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes EDA20%（wt）、 DIPA8%（wt）, dense H2SO42%
（wt）, add boric acid and absorbing liquid pH value be tuned into 6 or so, remaining is deionized water.Removed according to the invention described above amine process
SO in Claus tail gas2Typical technique handled.The operation temperature on absorption tower is：50 DEG C, pressure is：0.25MPa；Again
Giving birth to tower operation temperature is：110 DEG C, pressure is：0.2MPa.Effect is shown in Table one after purification.
Embodiment 3
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes EDA15%（wt）、 PEG5%（wt）, dense H2SO42%（wt）,
Absorbing liquid pH value is tuned into 6 or so by addition boric acid, and remaining is deionized water.Claus is removed according to the invention described above amine process
SO in tail gas2Typical technique handled.The operation temperature on absorption tower is：70 DEG C, pressure is：0.5MPa；The regeneration
Tower operation temperature is：130 DEG C, pressure is： 0.4MPa.Effect is shown in Table one after purification.
Embodiment 4
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes EDA20%（wt）、PEG8%（wt）, dense H2SO42%（wt）,
Absorbing liquid pH value is tuned into 6 or so by addition boric acid, and remaining is deionized water.Claus is removed according to the invention described above amine process
SO in tail gas2Typical technique handled.The operation temperature on absorption tower is：35 DEG C, pressure is：0.2MPa；Regenerator is grasped
It is as temperature：100 DEG C, pressure is：0.2MPa.Effect is shown in Table one after purification.
Embodiment 5
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes EDA15%（wt）、HEPZ5%（wt）, dense H2SO42%（wt）,
Absorbing liquid pH value is tuned into 6 or so by addition boric acid, and remaining is deionized water.Claus is removed according to the invention described above amine process
SO in tail gas2Typical technique handled.The operation temperature on absorption tower is：40 DEG C, pressure is：0.25 MPa；It is described again
Giving birth to tower operation temperature is：110 DEG C, pressure is：0.2 MPa.Effect is shown in Table one after purification.
Embodiment 6
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Absorbing liquid includes EDA 20%（wt）、HEPZ 8%（wt）, dense H2SO4 2%
（wt）, add boric acid and absorbing liquid pH value be tuned into 6 or so, remaining is deionized water.Removed according to the invention described above amine process
SO in Claus tail gas2Typical technique handled.The operation temperature on absorption tower is：40 DEG C, pressure is：0.25 MPa；Institute
Stating regenerator operation temperature is：110 DEG C, pressure is：0.2 MPa.Effect is shown in Table one after purification.
Comparative example
Certain Gas Purification Factory Claus tail gas composition is simulated, configures unstripped gas：SO2 1.10%、H2S 2.20%、CO2 3.10%、
H2O 32.50%, N261.1%（It is volume ratio）.Using certain Gas Purification Factory SCOT method handling process.Effect is shown in after purification
Table one.
One different absorbing liquids of table form to be contrasted with SCOT methods operating characteristics
The as shown by data of table one, can be by the SO in Claus tail gas using the absorbing liquid composition of the present invention2It is removed to 15mg/m3, take off
Sulphur efficiency significantly improves compared with SCOT method handling process.
Claims (9)
1. SO in one kind processing Claus tail gas2Absorbing liquid, it is characterised in that the absorbing liquid include 10 ~ 50%（wt）Have
Machine diamine, 1 ~ 5%（wt）Organic amine activating agent, 2 ~ 10%（wt）Organic amine reaction promoter and 50 ~ 85%（wt）Water.
2. absorbing liquid according to claim 1, it is characterised in that it is different that described organic diamine contains two alkalescence
Amine groups, the stronger amine groups of its neutral and alkali are absorbing SO2Before, first generate stable ammonium with organic diamine active agent response
Salt, the weaker amine groups of another alkalescence are used for SO2Absorption.
3. absorbing liquid according to claim 1, it is characterised in that described organic diamine activating agent be hydrochloric acid, sulfuric acid,
One or more in oxalic acid, acetic acid, boric acid or citric acid.
4. SO according to claim 12Absorbing liquid, it is characterised in that described organic amine reaction promoter is diisopropanolamine (DIPA)
（DIPA）, isopropylamine base ethanol（IPAE）, isopropylamine base isopropanol（IPAIP）, isobutyl amine ethanol（IBAE）, isobutyl amine third
Alcohol（IBAP）, isobutyl amine isopropanol（IBAIP）, tert-butylamine base propyl alcohol（TBAP）, tert-butylamine base isopropanol（TBAIP）, poly- second
Glycol 400（PEG400）, hydroxyethyl piperazine（HEPZ）, polyethylene glycol（PEG400）, morpholine（MOR）In one or more.
5. absorbing liquid according to claim 1, it is characterised in that total amine concentration is 12 ~ 60% in the absorbing liquid（wt）.
6. absorbing liquid according to claim 1, it is characterised in that it is 0.01 ~ 2.5% that concentration range is added in the absorbing liquid
（wt）Corrosion inhibiter, defoamer.
7. absorbing liquid according to claim 1, it is characterised in that the pH value of the absorbing liquid is controlled between 3-10.
A kind of 8. SO in any described absorbing liquid processing Claus tail gas using claim 1-82Method, it is characterised in that bag
Include following steps：
1）Claus tail gas initially enters tail gas burning furnace, and the sulphur of various forms is converted into SO at high temperature2；
2）Contain SO2Tail gas after incineration enter absorption tower after cooling, and absorbing liquid counter current contacting, the SO in tail gas2Absorbed
Liquid is absorbed, and the tail gas after purification can be discharged directly；
3）Rich in SO2Absorbing liquid enter regenerator, the poor amine liquid after steam stripping regeneration through heat exchange cool down after return absorption tower follow
Ring utilizes；
4）SO in regeneration gas2Butt, volume ratio reach more than 99.5%, high concentration SO2Regeneration gas is re-fed into Cross unit
Participate in reaction production sulphur.
9. according to the method for claim 9, it is characterised in that：The operation temperature on the absorption tower is：20 ~ 70 DEG C, pressure
For：0.1~0.5MPa；The regenerator operation temperature is：90 ~ 130 DEG C, pressure is：0.1~0.4MPa.
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| US20140294704A1 (en) * | 2013-03-29 | 2014-10-02 | The University Of Kentucky Research Foundation | Solvent and method for removal of an acid gas from a fluid stream |
| CN105214445A (en) * | 2014-06-05 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of amine absorbent for removing sulfur dioxide in gaseous mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1421264A (en) * | 2002-12-11 | 2003-06-04 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
| US20050034600A1 (en) * | 2003-08-13 | 2005-02-17 | Ravary Patrick M. | Low energy regenerable SO2 scrubbing process |
| CN1962032A (en) * | 2005-11-09 | 2007-05-16 | 南化集团研究院 | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide |
| CN103521035A (en) * | 2012-12-25 | 2014-01-22 | 北京博奇电力科技有限公司 | High-efficiency desulfurizing combined solvent |
| US20140294704A1 (en) * | 2013-03-29 | 2014-10-02 | The University Of Kentucky Research Foundation | Solvent and method for removal of an acid gas from a fluid stream |
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Application publication date: 20180403 |