CN102091503B - The chemical method of a kind of trapping, fixing and purification of carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxide - Google Patents
The chemical method of a kind of trapping, fixing and purification of carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxide Download PDFInfo
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- CN102091503B CN102091503B CN201110000875.8A CN201110000875A CN102091503B CN 102091503 B CN102091503 B CN 102091503B CN 201110000875 A CN201110000875 A CN 201110000875A CN 102091503 B CN102091503 B CN 102091503B
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Abstract
The invention provides the chemical method of a kind of trapping, chemistry fixing and purification of carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxide isothermal chamber gas, it is characterized in that this chemical method adopts organo-metallic compound and solvent as catching and chemical fixatives, organometallic complex is the complex of nitrogenous organo-bismuth and antimony organic.Solvent is organic solvent.This method to greenhouse gases can realize to catch and chemistry is fixed, form corresponding slaine; And selective gradient can be realized at different temperature resolve, thus a step realizes trapping and the purification of pure gas.Such trapping and fixative crystallized ability large, resolution speed is fast, and regeneration energy consumption is low, trapping and fixative is cheap and easy to get, prepare simply, stability is high and can repeatedly use.The present invention's greenhouse gases that can be widely used in flue gas, synthetic ammonia, natural gas, kiln gas etc. carry out catching and chemistry is fixed, and can a step realize purifying the enrichment of pure gas.
Description
[technical field]
The invention belongs to resource environment, chemical technology field, relate in particular to for carbon dioxide (CO
2), sulfur dioxide (SO
2), sulfur trioxide (SO
3) and nitrogen oxide (NO
x) the new and effective chemical absorbent of the fixing and purification of trapping, chemistry.
[background technology]
Carbon dioxide (CO
2) be topmost greenhouse gases on the current earth.Along with the generation of the industrial revolution and the progress of science and technology, CO
2discharge capacity also day by day increase, CO in air
2the too high greenhouse effects caused of isothermal chamber gas content bring to human being's production and life and have a strong impact on.On the other hand, CO
2it is carbon resource inexhaustible, nexhaustible on the earth.Along with a large amount of use of conventional carbon resource (fossil fuel) and the continuous rising of demand for energy, these carbon resources are just day by day exhausted, cause " carbon source crisis ".And the CO in air and water
2rich content, is about 3.67 × 10,600,000,000 tons, is equivalent to coal and oil phosphorus content about 10 times.Therefore, trapping, storage and recycling are discharged into a large amount of CO in air
2not only can reduce CO in air
2isothermal chamber gas content is also the important means alleviating " carbon source crisis ".
Directly to the CO that trapping is reclaimed
2carry out the CO of recycling requirement trapping
2gas purity is higher, thus relates to capture and separation CO
2etc. problem.The corresponding CO of exploitation has been attached great importance in countries in the world
2reclaim and purify and reutilization technology.CO is carried out for mobile emission source (automobile etc.)
2trapping separating difficulty is comparatively large, but for CO
2emission source (as thermal power plant, cement plant, steel mill, refinery etc.) is concentrated to carry out CO
2it is feasible and possible that trapping is separated, at present existing lot of documents report.Its trapping separation method mainly comprises absorption and separation method, absorption method, membrane separation process, cryogenic distillation process, hydrate, etc.In these methods, absorption and separation method is the method entering industrial-scale pilot, and the main absorbent of employing is monoethanolamine (MEA process).Although MEA process and improve one's methods there is the features such as infiltration rate is fast, absorbability is strong, equipment size is little, its amine degradation, burn into resolution temperature is high, energy consumption is higher etc., and problem is not solved.In addition, current industrial best desulfur technology can remove the sulfurous gas of about 95%, and best denitration technology can remove the nitrogen-containing oxide gas of about 85%, removes more difficult completely.Therefore, even if CO
2concentrated emission source through process such as desulphurization and denitrations, but passes through the CO of its tail gas institute enrichment
2the component of gas is still very complicated; Containing a small amount of sulfur dioxide (SO
2), sulfur trioxide (SO
3) and nitrogen oxide (NO
x) etc. gas, these gases be also part cause trap CO
2the not high reason of purity.Due to the CO containing highly acid gas
2purification for gas cost is higher, and its recycling receives larger restriction, so part can only be buried in seabed, result in the serious waste of carbon resource.In addition through desulfurization (SO
2and SO
3), denitration (NO
x), decarburization (CO
2) etc. three process result also in the rising of energy consumption, cause secondary emission.Thus the concern that a step realizes desulphurization and denitration, the technology of decarburization is subject to people day by day, but its regeneration energy consumption is high, and the gas of regeneration can not realize gradient and resolve, and again will be separated, thus not have economic use value to the recycling of C1 resource.Therefore, multiple greenhouse gases (CO is trapped to how realizing a step
2, SO
2, SO
3and NO
x), and then Gradient Solution separates out pure gas species, thus a step realizes multiple gases trapping, the new technologies such as pure gas purification enrichment propose new requirement.
Utilize organometallic complex fixation of C O in recent years
2have been reported, mainly concentrate on lanthanum, nickel, the metals such as copper.And the complex such as organic metal bismuth and organic metal antimony is at fixation of C O
2the application report of aspect is few, mainly concentrates on the complex containing pincer part.In addition, also there is a lot of problem in these methods, as: can only to single CO
2absorb, can not realize the enrichment purification of multiple gases, and absorption efficiency is lower, acceptance condition is harsh, and regeneration energy consumption is high, and reusing is poor, complexes stability difference etc.Applicant its in publication number disclosed in 17 days September in 2008 be CN101264415A, it is entitled as in the patent application of " a kind of novel chemical absorbent of trapping and recovering carbon dioxide ", describe the oxide of a kind of novel organo-bismuth and antimony organic, find that this kind of complex can well chemical fixation of C O under the acting in conjunction of solvent
2.Recently we synthesized again series of new containing 5,6,7,12-[c, f] [1,5]-nitrogen bismuth (antimony) octene skeleton complex and find that this kind of complex is stablized air and water, and we also find that this kind of complex all has good catalytic effect to a series of organic synthesis.Find based on existing bibliographical information and our research, this kind of compound containing above-mentioned skeleton is applied to CO at imagination by us
2the chemistry of isothermal chamber gas is fixed and purifies perhaps significant.
Applicant is CN101508704A at its publication number disclosed in 19 days Augusts in 2009, the patent that it is entitled as " organic bismuth ion compound and preparation and application thereof containing bridge nitrogen atom ligand " and its in publication number disclosed in 30 days September in 2009 be CN101544672A be entitled as in the patent application of " antimony organic ionic compound and preparation and application thereof containing bridge nitrogen atom ligand ", describe the muriatic synthesis of two kinds of organometallic complexs, organometallic complex in the application can be obtained as CO using the chloride of these two kinds of complexs and corresponding alkali reaction
2, SO
2, SO
3, NO
xthe new and effective chemical absorbent of the fixing and purification of trapping, chemistry, develops a kind of brand-new trapping, fixing and purification CO
2, SO
2, SO
3, NO
xchemical method, realize a step and trap multiple greenhouse gases, then Gradient Solution separates out pure gas species, theory and practice is all feasible.
[summary of the invention]
The object of the present invention is to provide a kind of brand-new trapping, fixing and purification CO
2, SO
2, SO
3, NO
xchemical method, to improve CO
2, SO
2, SO
3, NO
xtrapping, the efficiency of resolving and purifying, provide CO
2, SO
2, SO
3, NO
xpurity, reduce reclaim CO
2, SO
2, SO
3, NO
xenergy consumption, improve trapping, fixing and resolve the selective of purification above-mentioned gas absorbent and can reusing.
To achieve the above object of the invention, the present invention proposes following technical scheme:
A kind of brand-new trapping, fixing and purification CO
2, SO
2, SO
3, NO
xchemical method, be take organic solvent as solvent, to be trapping, fixing and cleanser containing the organo-bismuth of bridge nitrogen atom ligand and the complex of antimony organic.
In above-mentioned synthetic method, described organo-metallic compound is organo-bismuth complex and the organic stibium complex with structural formula I:
Wherein, described complex be a class novel containing the organometallic complex of bridge nitrogen atom ligand, the structural formula of described part is [(R
1) (R
2) (R
3) (R
4) PhCH
2] N [R '] [CH
2ph (R
5) (R
6) (R
7) (R
8)], wherein R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8for the substituting group on phenyl ring; R ' is the substituting group on nitrogen-atoms; Metal center (M
3+) be bismuth (Bi
3+) and antimony (Sb
3+).M
3+with M
3+be connected by oxygen group elements; And in such complex, M
3-except being formed except covalent bond with the carbon atom of two in part, also form coordinate bond with the nitrogen-atoms in part, with M
3+covalent bond is formed with chalcogen atom.
In above-mentioned synthetic method, the substituent R of described part
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, for identical on phenyl ring or not identical alkyl (C0-C20) or aryl (C6-C20) and containing different heteroatomic various substituted radical, wherein preferably H, methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl or naphthyl.
In above-mentioned synthetic method, the substituent R of described part ' for alkyl (C0-C20) or aryl (C6-C20) and containing different heteroatomic various substituted radical, wherein preferable methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl.
In above-mentioned synthetic method, described oxygen group elements are oxygen, sulphur, selenium and tellurium (O, S, Se, Te), wherein preferred oxygen and sulphur.
In above-mentioned synthetic method, described organo-metallic compound is obtained by reacting in organic solvent and water by organic metal chloride and corresponding alkali.
In above-mentioned synthetic method, described alkali is inorganic base and alkali metal salt; Wherein, the preferred potassium hydroxide of inorganic base, NaOH, cesium hydroxide; Alkaline, inorganic salts is alkali metal salt, wherein preferred vulcanized sodium, potassium sulfide, sodium selenide, potassium selenide, telluride sodium, telluride potassium, sodium carbonate, sodium acid carbonate, potash, saleratus, cesium carbonate.
In above-mentioned synthetic method, the described organic solvent preparing organometallic complex is polarity and non-polar solven, wherein preferred carrene, chloroform, benzene, toluene.
In above-mentioned synthetic method, the described reaction temperature preparing organometallic complex is 0-120 DEG C, and reaction time 0.5-24h, reacts and carry out under inert gas shielding, wherein inert gas preferred nitrogen and argon gas.
In above-mentioned synthetic method, described method can absorb CO
2, SO
2, SO
3, NO
xin gas wherein one or more, preferentially catch acid stronger species of gases under the same conditions.
In above-mentioned synthetic method, described in catch with chemical rigid condition be the concentration of organometallic complex be 0.1-10mol/L; Solvent is organic solvent, gas pressure 0.5-10MPa, and temperature is-20-120 DEG C, and one way capture time is 5min-24h; Wherein organic solvent is polarity and non-polar organic solvent, preferred toluene, carrene, methyl alcohol, ethanol, ethylene glycol.
In above-mentioned synthetic method, the condition of described parsing is: at 0-400 DEG C, vacuum (0.001-0.01MPa) adds Thermal desorption 0.5-24h, and wherein different according to heating-up temperature, the species of gases that Gradient Solution separates out is different.
In above-mentioned synthetic method, the gas of catching and fix can be parsed by change condition by described method, realizes gradient at different temperatures and resolves.
Absorbent of the present invention is to CO
2, SO
2, SO
3, NO
xabsorbability large, absorb and resolution speed soon, to different CO
2, SO
2, SO
3, NO
xselective trapping and purification can be carried out Deng mist, its regeneration temperature and regeneration energy consumption low, to equipment free of losses, and absorbent is cheap and easy to get, nontoxic pollution-free, preparation simply, not halogen-containing element, stability are high and can repeatedly use.The present invention can be widely used in the CO of the process gas such as flue gas, synthetic ammonia, natural gas, kiln gas
2trapping reclaiming clean.In addition, the present invention is not limited only to CO
2trapping purification, can also SO be used for
2, SO
3, NO
xtrapping Deng gas purifies.
[accompanying drawing explanation]
The synthesis path figure of organometallic complex provided by the invention shown in Fig. 1.CO provided by the invention shown in Fig. 2
2, SO
2, SO
3, NO
xtrapping and resolving.
[detailed description of the invention]
The synthesis path of organometallic complex provided by the present invention; refer to accompanying drawing 1: under inert gas shielding; to insert in reaction vessel as raw material organic metal chloride II; add organic solvent stirring to make it to dissolve completely; then aqueous slkali is added; under the environment of 0-120 DEG C, react 0.5-24h, namely obtain after having reacted or namely obtain target organometallic complex I through super-dry post processing.
CO provided by the present invention
2, SO
2, SO
3, NO
xtrapping and the path of parsing, refer to accompanying drawing 2: insert in reaction vessel using the organometallic complex II as absorbent, solvent is organic solvent, and the concentration of organometallic complex is 0.1-10mol/L; Pass into CO
2, SO
2, SO
3, NO
xin one or more gases to be captured, pressure 0.5-10MPa; Trapping temperature is-20-120 DEG C, and the one way trapping time is 5min-24h; Namely corresponding organic metal salt is obtained after having reacted.After trapping process completes, at 0-400 DEG C, vacuum (0.001-0.01MPa) adds Thermal desorption 0.5-24h, and wherein different according to intensification heating-up temperature, the species of gases that Gradient Solution separates out is different.
Below in conjunction with specific embodiment, the present invention will be further described:
embodiment 1
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be hydrogen, R ' is cyclohexyl, and X is oxygen, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (He/CO of 90%
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 25 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, then utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2concentration.Almost CO is can't detect in tail gas
2, show CO
2capture rate close to 100%, show that organo-metallic compound all changes into carbonate, organometallic complex conversion ratio and selective all close to 100%.After trapping process completes, at 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity be 100%, organic metal carbonate all changes into corresponding organometallic complex, and repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 2
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be hydrogen, R ' is cyclohexyl, and X is oxygen, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (SO of 90%
2/ CO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 45 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, then utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and SO
2concentration.Almost SO is can't detect in tail gas
2, be all CO
2, show that organo-metallic compound all changes into sulphite and carbonate, organometallic complex conversion ratio is close to 100%; Show SO
2capture rate close to 100%, the purifying rate of carbon dioxide is close to 100%.After trapping process completes, at 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex, and at continuing to increase the temperature to 250 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 3
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be hydrogen, R ' is methyl, and X is oxygen, and M is bismuth) 10.0g, benzene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 80%
2/ NO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 45 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, then utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and NO
2concentration.Almost NO is can't detect in tail gas
2, be all CO
2, show NO
2capture rate close to 100%, the purifying rate of carbon dioxide is close to 100%, and organo-metallic compound all changes into carbonate and nitrate, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 80 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, wherein different according to temperature, NO
2all solutions separates out, and obtains NO
2purity close to 100%, organic metal nitrate all changes into corresponding organometallic complex, and at continuing to increase the temperature to 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 4
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be methyl, R ' is phenyl, and X is oxygen, and M is antimony) 10.0g, toluene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 50%
2/ SO
3), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 45 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and SO
3concentration.Almost SO is can't detect in tail gas
3, be all CO
2, show SO
3capture rate close to 100%, CO
2purifying rate close to 100%, organo-metallic compound all changes into sulfate and carbonate, and organometallic complex conversion ratio is close to 100%.After trapping process completes, at 100 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, wherein different according to temperature, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex, and at continuing to increase the temperature to 300 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
3all solutions separates out, and obtains SO
3purity close to 100%, organic metal sulfate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 5
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4be H, R
5, R
6, R
7, R
8be methyl, R ' is the tert-butyl group, and X is oxygen, and M is bismuth) 10.0g, ethylene glycol 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 50%
2/ NO), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is-20 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2with the concentration of NO.Almost can't detect NO in tail gas, is all CO
2, show that the capture rate of NO is close to 100%, CO
2purifying rate close to 100%, organo-metallic compound all changes into nitrite and carbonate, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 60 DEG C, vacuum (0.002MPa) adds Thermal desorption 10h, NO all solutions separates out, obtain the purity of NO close to 100%, organic metal nitrite all changes into corresponding organometallic complex, at continuing to increase the temperature to 170 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 6
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4be H, R
5, R
6, R
7, R
8be methyl, R ' is the tert-butyl group, and X is sulphur, and M is bismuth) 10.0g, ethanol 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 50%
2/ NO/SO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 0 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2, SO
2with the concentration of NO.Almost NO and SO is can't detect in tail gas
2, be all CO
2, show NO and SO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into sulphite and nitrite, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 80 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, and NO all solutions separates out, and obtains the purity of NO close to 100%, and organic metal nitrite all changes into corresponding organometallic complex; At continuing to increase the temperature to 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, has no CO
2all solutions separates out, and shows that organometallic complex does not get transformed into carbonate; At continuing to increase the temperature to 290 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 7
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4be H, R
5, R
6, R
7, R
8be ethyl, R ' is phenyl, and X is sulphur, and M is bismuth) 10.0g, chloroform 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 50%
2/ NO/SO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 0 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2, SO
2with the concentration of NO.Almost NO and SO is can't detect in tail gas
2, be all CO
2, show NO and SO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into sulphite and nitrite, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 120 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, wherein different according to temperature, NO all solutions separates out, obtain the purity of NO close to 100%, organic metal nitrite is all from newly changing into corresponding organometallic complex, and at continuing to increase the temperature to 250 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite is all from newly changing into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 8
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, be H, R
8for phenyl, R ' is methyl, and X is sulphur, and M is bismuth) 10.0g, methyl alcohol 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 60%
2/ SO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 0 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and SO
2concentration.Almost SO is can't detect in tail gas
2, be all CO
2, show SO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into sulphite, shows that organometallic complex conversion ratio is close to 100%, selective 100%.After trapping process completes, at 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, wherein different according to temperature, has no CO
2parse, show that organometallic complex does not get transformed into carbonate, all change into sulphite.At continuing to increase the temperature to 280 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite is all from newly changing into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 9
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, be H, R
8for phenyl, R ' is methyl, and X is sulphur, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 40%
2/ NO
2), CO
2the pressure of gaseous mixture is 4.0MPa, and temperature is 10 DEG C, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and NO
2concentration.Almost NO is can't detect in tail gas
2, be all CO
2, show NO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into nitrate, shows that organometallic complex conversion ratio is close to 100%, selective close to 100%.After trapping process completes, at 130 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, NO
2all solutions separates out, and obtains NO
2purity close to 100%, organic metal nitrite is all from newly changing into corresponding organometallic complex; At continuing to increase the temperature to 250 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, has no CO
2parse, show that organometallic complex does not get transformed into carbonate.Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 10
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be methyl, R ' is the tert-butyl group, and X is selenium, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 50%
2/ SO
3), CO
2the pressure of gaseous mixture is 3.4MPa, and temperature is 20 DEG C, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and SO
3concentration.Almost SO is can't detect in tail gas
3, be all CO
2, show SO
3capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into sulfate, shows that organometallic complex conversion ratio is close to 100%, selective close to 100%.After trapping process completes, at 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, wherein different according to temperature, has no CO
2parse, show that organometallic complex does not get transformed into carbonate, all change into sulfate.At continuing to increase the temperature to 300 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
3all solutions separates out, and obtains SO
3purity close to 100%, organic metal sulfate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 11
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be H, R ' is normal-butyl, and X is oxygen, and M is antimony) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 40%
2/ SO
2), CO
2the pressure of gaseous mixture is 4.0MPa, and temperature is 10 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and NO
2concentration.Almost SO is can't detect in tail gas
2, be all CO
2, show SO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into sulphite and carbonate, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex, and at continuing to increase the temperature to 250 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 12
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be H, R ' is phenyl, and X is oxygen, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 60%
2/ SO
2/ SO
3/ NO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 10 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2, SO
2, SO
3and NO
2concentration.Almost SO is can't detect in tail gas
2, SO
3and NO
2, be all CO
2, show SO
2, SO
3, NO
2capture rate close to 100%, CO
2purifying rate close to 100%.Organo-metallic compound all changes into carbonate, sulphite, sulfate and nitrate, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 60 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, NO
2all solutions separates out, and obtains NO
2purity close to 100%, organic metal nitrate all changes into corresponding organometallic complex; At continuing to increase the temperature to 150 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate is all from newly changing into corresponding organometallic complex; At continuing to increase the temperature to 250 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
2all solutions separates out, and obtains SO
2purity close to 100%, organic metal sulphite all changes into corresponding organometallic complex; At continuing to increase the temperature to 300 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, SO
3all solutions separates out, and obtains SO
3purity close to 100%, organic metal sulfate is all from newly changing into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 13
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
4, R
5, R
6, R
8be H, R
3, R
7for methyl, R ' is phenyl, and X is oxygen, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 10%
2/ He), CO
2the pressure of gaseous mixture is 10.0MPa, and temperature is 10 DEG C, airtight air inlet and gas outlet, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2concentration.Almost CO is can't detect in tail gas
2, show CO
2capture rate close to 100%.CO
2all change into carbonate, show organometallic complex trapping CO
2selective close to 100%.After trapping process completes, at 100 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 14
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
4, R
5, R
6, R
8be H, R
3, R
7for phenyl, R ' is methyl, and X is oxygen, and M is antimony) 10.0g, chloroform 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 40%
2/ O
2), CO
2the pressure of gaseous mixture is 10.0MPa, and temperature is 120 DEG C, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and O
2concentration.Almost CO is can't detect in tail gas
2, be all O
2, show CO
2capture rate close to 100%, O
2purifying rate close to 100%.Organo-metallic compound all changes into carbonate, shows that organometallic complex conversion ratio is close to 100%.After trapping process completes, at 100 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, organic metal carbonate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
embodiment 15
Organometallic complex I (R is added successively in the 100mL stainless steel cauldron being furnished with air inlet and gas outlet
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be H, R ' is normal-butyl, and X is oxygen, and M is bismuth) 10.0g, carrene 5mL, sealed reactor, passes into CO after stirring 5min
2concentration is the gaseous mixture (CO of 10%
2/ O
2/ N
2), CO
2the pressure of gaseous mixture is 10.0MPa, and temperature is 50 DEG C, stirring reaction 1h, utilizes CO in the gas chromatograph detection of dynamic tail gas with thermal conductivity cell detector
2and O
2concentration.Almost CO is can't detect in tail gas
2, be all N
2and O
2, CO
2all change into carbonate, show CO
2conversion ratio is close to 100%, CO
2capture rate close to 100%.After trapping process completes, at 100 DEG C, vacuum (0.001MPa) adds Thermal desorption 10h, CO
2all solutions separates out, and obtains CO
2purity close to 100%, CO
2purifying rate close to 100%, organic metal carbonate all changes into corresponding organometallic complex; Repeatedly absorb and resolve 10 times, the structure of organometallic complex is not destroyed, and absorption and analytic ability do not decline.
In order to further illustrate the superiority of the inventive method, select following absorption system as a comparison case.
comparative example 1
In the 100mL stainless steel cauldron being furnished with air inlet and gas outlet, add MEA 10.0g, carrene 5mL successively, sealed reactor, after stirring 5min, pass into CO
2concentration is the gaseous mixture (CO of 40%
2/ SO
2/ SO
3/ NO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 20 DEG C, stirring reaction 1h.Utilize with CO in the gas chromatograph detection of dynamic tail gas of thermal conductivity cell detector
2, SO
2, SO
3and NO
2concentration.SO is detected in tail gas
2, SO
3, NO
2and CO
2, show the poor selectivity of MEA, CO
2purifying rate close to 73%.In addition, owing to there being the existence of highly acid gas, the structure of absorbent there occurs change, and the energy consumption of regeneration significantly rises, and part there occurs amine degradation simultaneously.
comparative example 2
In the 100mL stainless steel cauldron being furnished with air inlet and gas outlet, add 2-(dimethylamino)-ethanol (DEAE) 10.0g, carrene 5mL successively, sealed reactor, after stirring 5min, pass into CO
2concentration is the gaseous mixture (CO of 40%
2/ SO
2/ SO
3/ NO
2), CO
2the pressure of gaseous mixture is 3.0MPa, and temperature is 20 DEG C, stirring reaction 1h.Utilize with CO in the gas chromatograph detection of dynamic tail gas of thermal conductivity cell detector
2, SO
2, SO
3and NO
2concentration.SO is detected in tail gas
2, SO
3, NO
2and CO
2, show the poor selectivity of MEA, CO
2purifying rate close to 83%; In addition, owing to there being the existence of highly acid gas, the structure of absorbent there occurs change, and the energy consumption of regeneration significantly rises, and part there occurs amine degradation simultaneously.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (11)
1. trap, the chemical method of fixing and purification of carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxide, it is characterized in that this chemical method adopts organo-metallic compound and solvent as catching and chemical fixatives; Wherein, described organo-metallic compound is organo-bismuth complex and the organic stibium complex with structural formula I:
Such complex be a class novel containing the organometallic complex of bridge nitrogen atom ligand, the structural formula of its part is [(R
1) (R
2) (R
3) (R
4) PhCH
2] N [R '] [CH
2ph (R
5) (R
6) (R
7) (R
8)], wherein R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8for identical on phenyl ring or not identical substituting group; R ' is the substituting group on nitrogen-atoms; Metal center M
3+for Bi
3+and Sb
3+; M
3+with M
3+be connected by oxygen group elements; And in such complex, M
3+except being formed except covalent bond with the carbon atom of two in part, also form coordinate bond with the nitrogen-atoms in part, with M
3+covalent bond is formed with chalcogen atom.
2. method according to claim 1, is characterized in that, the substituent R of described part
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, the R ' aryl that is the alkyl within identical or not identical C20 or C6-C20, and with the heteroatomic various substituted radical of difference.
3. method according to claim 2, is characterized in that, the substituent R of described part
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R ' is H, methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl or naphthyl; Described oxygen group elements are oxygen, sulphur, selenium or tellurium.
4. method according to claim 2, is characterized in that, described oxygen group elements are oxygen or sulphur.
5. method according to claim 1, is characterized in that, described organo-metallic compound in organic solvent and water, reacts obtained by organic metal chloride and corresponding alkali; Its reaction condition is under inert gas shielding, reaction temperature 0-120 DEG C, reaction time 0.5-24h.
6. method according to claim 5, is characterized in that, described alkali is inorganic base and alkaline, inorganic salts; Wherein, inorganic base is selected from lithium hydroxide, NaOH, potassium hydroxide or cesium hydroxide; Alkaline, inorganic salts is selected from vulcanized sodium, potassium sulfide, sodium selenide, potassium selenide, telluride sodium, telluride potassium, sodium carbonate, sodium acid carbonate, potash, saleratus or cesium carbonate; Described organic solvent is polarity and non-polar solven, is to be selected from carrene, chloroform, benzene or toluene; Described inert gas is selected from nitrogen or argon gas.
7. method according to claim 1, is characterized in that, described method is at trapping CO
2, SO
2, SO
3, NO
xduring one or more in gas, the acid stronger species of gases of preferential trapping under the same conditions.
8. the method according to claim 1 or 7, it is characterized in that, described method is further comprised and is parsed by the gas of catching and fix by change condition, and the step that gradient is resolved can be realized at different temperatures, the condition of described parsing is: at 0-400 DEG C, pressure 0.001-0.01Mpa, adds Thermal desorption 0.5-24h.
9. method according to claim 1, is characterized in that, described in catch with chemical rigid condition be the concentration of organometallic complex be 0.1-10mol/L; Solvent is organic solvent, gas pressure 0.5-10MPa, and temperature is-20-120 DEG C, and one way capture time is 5min-24h.
10. the method according to claim 1 or 9, is characterized in that, described organic solvent is organic polar solvent or non-polar solven.
11. methods according to claim 10, is characterized in that, described organic solvent is selected from toluene, carrene, methyl alcohol, ethanol or ethylene glycol.
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| CN102921273B (en) * | 2012-11-05 | 2015-02-18 | 中国船舶重工集团公司第七一八研究所 | Mine carbon dioxide absorbent and preparation method thereof |
| US20140150652A1 (en) * | 2012-11-30 | 2014-06-05 | Alstom Technology Ltd. | Post absorber scrubbing of so3 |
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| CN113348030A (en) * | 2019-01-28 | 2021-09-03 | 乔治·罗伯特·理查森 | CO2、NOxAnd SO2Chemical sealing of |
| WO2020241089A1 (en) * | 2019-05-28 | 2020-12-03 | 株式会社神戸製鋼所 | Gas treatment method, and gas treatment device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5428274A (en) * | 1977-08-04 | 1979-03-02 | Asahi Chem Ind Co Ltd | Treating method for exhaust combustion gas |
| JPS54123574A (en) * | 1978-03-17 | 1979-09-25 | Matsushita Electric Ind Co Ltd | Exhaust gas treating agent |
| US4186179A (en) * | 1977-05-30 | 1980-01-29 | Toray Industries, Inc. | Process for producing oxidized or carbon fibers |
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| US4186179A (en) * | 1977-05-30 | 1980-01-29 | Toray Industries, Inc. | Process for producing oxidized or carbon fibers |
| JPS5428274A (en) * | 1977-08-04 | 1979-03-02 | Asahi Chem Ind Co Ltd | Treating method for exhaust combustion gas |
| JPS54123574A (en) * | 1978-03-17 | 1979-09-25 | Matsushita Electric Ind Co Ltd | Exhaust gas treating agent |
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