CN102091503A - Chemical method for trapping, fixing and purifying carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxides - Google Patents
Chemical method for trapping, fixing and purifying carbon dioxide, sulfur dioxide, sulfur trioxide and nitrogen oxides Download PDFInfo
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- CN102091503A CN102091503A CN2011100008758A CN201110000875A CN102091503A CN 102091503 A CN102091503 A CN 102091503A CN 2011100008758 A CN2011100008758 A CN 2011100008758A CN 201110000875 A CN201110000875 A CN 201110000875A CN 102091503 A CN102091503 A CN 102091503A
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Abstract
The invention provides a chemical method for trapping, chemically fixing and purifying greenhouse gases such as carbon dioxide, sulfur dioxide, sulfur trioxide, nitrogen oxides and the like, which is characterized by adopting an organic metal compound and a solvent as trapping and chemical fixing agents, wherein the organic metal compound is a coordination compound of nitrogenous organic bismuth and organic antimony; and the solvent is an organic solvent. By means of the method, the trapping and chemical fixing of all the greenhouse gases can be realized to form corresponding metal salts; and at different temperatures, selective gradient analysis can be realized so that the trapping and purification of single gas is further realized. The trapping and fixing agents have high fixing capacity, high analytic speed, low regeneration energy consumption and low price, are easy and simple to prepare, have high stability and can be used repeatedly. The chemical method can be widely used for carrying out trapping and chemical fixing on the greenhouse gases in flue gas, synthesis ammonia, natural gas, kiln gas and the like and can realize enrichment purification of the single gas in one step.
Description
[technical field]
The invention belongs to resource environment, chemical technology field, relate in particular to and be used 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 capture, chemical fixation and purification.
[background technology]
Carbon dioxide (CO
2) be topmost greenhouse gases on the present earth.Along with the generation and the progress of science and technology of the industrial revolution, CO
2Discharge capacity also increase CO in the atmosphere day by day
2The too high greenhouse effects that cause of isothermal chamber gas content have brought for 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 uses of conventional carbon resource (fossil fuel) and the continuous rising of demand for energy, these carbon resources are exhausted just day by day, cause " carbon source crisis ".And the CO in the big G﹠W
2Content is abundant, is about 3.67 * 10,600,000,000 tons, is equivalent to coal and oil phosphorus content about 10 times.Therefore, capture, storage and recycling are discharged into a large amount of CO in the atmosphere
2Not only can reduce CO in the atmosphere
2The isothermal chamber gas content also is an important means of alleviating " carbon source crisis ".
Directly to capturing the CO that reclaims
2Carry out the CO that the recycling requirement captures
2Gas purity is higher, captures and separation of C O thereby relate to
2Etc. problem.Exploitation corresponding C O has been attached great importance in countries in the world
2Recovery and purification and reutilization technology.Carry out CO for mobile emission source (automobile etc.)
2It is bigger to capture separating difficulty, but for CO
2Concentrate emission source (as thermal power plant, cement plant, steel mill, refinery etc.) to carry out CO
2It is feasible and possible capturing separation, existing at present lot of documents report.It captures separation method and mainly comprises absorption and separation method, absorption method, membrane separation process, low temperature distillation method, hydrate, or the like.In these methods, the absorption and separation method is the method that enters industrial-scale pilot, and the main absorbent of employing is monoethanolamine (MEA process).Although MEA process and improve one's methods and have characteristics such as infiltration rate is fast, absorbability is strong, equipment size is little,, its amine degradation, burn into resolution temperature height, energy consumption are not solved than problems such as height.In addition, industrial best desulfur technology can be removed the sulfurous gas about 95% at present, and best denitration technology can be removed the nitrogen-containing oxide gas about 85%, removes the comparison difficulty fully.Therefore, even CO
2Concentrated emission source has passed through processing such as desulfurization, denitration, but passes through the CO of its tail gas institute enrichment
2The component of gas is still very complicated; Contain a spot of sulfur dioxide (SO
2), sulfur trioxide (SO
3) and nitrogen oxide (NO
X) to wait gas, these gases also be that part causes the CO that captures
2The not high reason of purity.Owing to contain the CO of highly acid gas
2The purification for gas cost is higher, and its recycling has been subjected to bigger restriction, so part can only be buried in the seabed, has caused the serious waste of carbon resource.Pass through desulfurization (SO in addition
2And SO
3), denitration (NO
X), decarburization (CO
2) wait three process also to cause the rising of energy consumption, cause secondary emission.Thereby one the step realize that the technology of desulfurization, denitration, decarburization is subjected to people's attention day by day, but its regeneration energy consumption height, the gas of regeneration can not realize that gradient resolves, and separate again, thereby the utilization again of C1 resource is not had economic use value.Therefore, to how realizing that a step captures multiple greenhouse gases (CO
2, SO
2, SO
3And NO
X), and then gradient parses the pure gas species, thus a step realize that multiple gases captures, new technologies such as pure gas purification enrichment have proposed new requirement.
Utilize organometallic complex fixation of C O in recent years
2Existing report mainly concentrates on metals such as lanthanum, nickel, copper.And complexs such as organic metal bismuth and organic metal antimony are at fixation of C O
2The application report of aspect is few, mainly concentrates on the complex that contains the pincer part.In addition, also there are a lot of problems in these methods, as: can only be to single CO
2Absorb, can not realize that the enrichment of multiple gases purifies, and absorption efficiency is lower, the acceptance condition harshness, regeneration energy consumption height, reuse is poor, complexes stability difference etc.Applicant its on September 17th, 2008 disclosed publication number be CN101264415A, it is entitled as in the patent application of " a kind of novel chemical absorbent of trapping and recovering carbon dioxide ", put down in writing a kind of novel organo-bismuth and the oxide of antimony organic, found that this class complex can well chemical fixation CO under the acting in conjunction of solvent
2We have synthesized again and a series ofly novel have contained 5,6,7 recently, 12-[c, f] [1,5]-nitrogen bismuth (antimony) octene skeleton complex and find that this class complex is stable to empty G﹠W, and we find that also this class complex all has good catalytic effect to a series of organic synthesis.Discover that based on existing literature report and we we are applied to CO with the compound that this class contains above-mentioned skeleton at imagination
2The chemical fixation of isothermal chamber gas and purification are perhaps significant.
Applicant its on August 19th, 2009 disclosed publication number be CN101508704A, the patent that it is entitled as " contain the organic bismuth ion compound of bridge nitrogen atom ligand and preparation thereof and use " and its on September 30th, 2009 disclosed publication number be in the patent application that is entitled as " containing antimony organic ionic compound and the preparation and the application of bridge nitrogen atom ligand " of CN101544672A, put down in writing the muriatic synthetic of two kinds of organometallic complexs, can obtain organometallic complex among the application as CO with the chloride of these two kinds of complexs and corresponding alkali
2, SO
2, SO
3, NO
XThe new and effective chemical absorbent of capture, chemical fixation and purification is developed a kind of brand-new capture, fixing and purification CO
2, SO
2, SO
3, NO
XChemical method, realize that a step captures multiple greenhouse gases, gradient parses the pure gas species then, all is feasible in theory and practice.
[summary of the invention]
The object of the present invention is to provide a kind of brand-new capture, fixing and purification CO
2, SO
2, SO
3, NO
XChemical method, to improve CO
2, SO
2, SO
3, NO
XThe efficient that captures, resolves and purify provides CO
2, SO
2, SO
3, NO
XPurity, reduce to reclaim CO
2, SO
2, SO
3, NO
XEnergy consumption, but improve to capture, fixing and resolve selectivity and the reuse that purifies the above-mentioned gas absorbent.
To achieve the above object of the invention, the present invention proposes following technical scheme:
A kind of brand-new capture, fixing and purification CO
2, SO
2, SO
3, NO
XChemical method, be to be solvent with the organic solvent, be capture, fixing and cleanser with the complex of the organo-bismuth that contains bridge nitrogen atom ligand and antimony organic.
In the above-mentioned synthetic method, described organo-metallic compound is organo-bismuth complex and the organic stibium complex with structural formula I:
Wherein, described complex is the novel organometallic complex that contains bridge nitrogen atom ligand of a class, and 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)], R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be the substituting group on the phenyl ring; R ' is the substituting group on the nitrogen-atoms; Metal center (M
3+) be bismuth (Bi
3+) and antimony (Sb
3+).M
3+With M
3+Be to link to each other by oxygen group elements; And in such complex, M
3-Except that with part in two carbon atoms form the covalent bonds, also with part in nitrogen-atoms form coordinate bond, with M
3+Form covalent bond with the chalcogen atom.
In the 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 alkyl (C0-C20) or aryl (C6-C20) identical or inequality on the phenyl ring and contain different heteroatomic various substituted radicals, wherein preferred H, methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl or naphthyl.
In the above-mentioned synthetic method, the substituent R of described part ' for alkyl (C0-C20) or aryl (C6-C20) and contain different heteroatomic various substituted radicals, wherein preferable methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl.
In the above-mentioned synthetic method, described oxygen group elements be oxygen, sulphur, selenium and tellurium (O, S, Se, Te), wherein preferred oxygen and sulphur.
In the above-mentioned synthetic method, described organo-metallic compound reacts in organic solvent and water by organic metal chloride and corresponding alkali and obtains.
In the 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 an alkali metal salt, wherein preferred vulcanized sodium, potassium sulfide, sodium selenide, potassium selenide, tellurium sodium, tellurium potassium, sodium carbonate, sodium acid carbonate, potash, saleratus, cesium carbonate.
In the above-mentioned synthetic method, the organic solvent that described preparation organometallic complex is used is polarity and non-polar solven, wherein preferred carrene, chloroform, benzene, toluene.
In the above-mentioned synthetic method, the reaction temperature of described preparation organometallic complex is 0-120 ℃, and reaction time 0.5-24h is reflected under the inert gas shielding and carries out, wherein inert gas preferred nitrogen and argon gas.
In the above-mentioned synthetic method, described method can absorb CO
2, SO
2, SO
3, NO
XIn the gas wherein one or more, preferentially catch acid stronger species of gases under the same conditions.
In the above-mentioned synthetic method, described catch with the chemical fixation condition be that the concentration of organometallic complex is 0.1-10mol/L; Solvent is an organic solvent, gas pressure 0.5-10MPa, and temperature is-20-120 ℃, the 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 the above-mentioned synthetic method, the condition of described parsing is: resolve 0.5-24h in 0-400 ℃ of following vacuum (0.001-0.01MPa) heating, wherein according to the heating-up temperature difference, the species of gases that gradient parses is different.
In the above-mentioned synthetic method, described method can parse by the gas that the change condition will be caught and fix, and realizes the gradient parsing under different temperatures.
Absorbent of the present invention is to CO
2, SO
2, SO
3, NO
XAbsorbability big, absorb and resolution speed fast, to different CO
2, SO
2, SO
3, NO
XCan carry out that selectivity captures and purify Deng mist, its regeneration temperature and regeneration energy consumption are low, to the equipment free of losses, and absorbent is cheap and easy to get, nontoxic pollution-free, preparation simply, not halogen-containing element, stability is high and can be repeatedly used.The present invention can be widely used in the CO of process gas such as flue gas, synthetic ammonia, natural gas, kiln gas
2Capture reclaiming clean.In addition, the present invention is not limited only to CO
2Capture purify, can also be used for SO
2, SO
3, NO
XCapture Deng gas purifies.
[description of drawings]
Shown in Figure 1 is the synthesis path figure of organometallic complex provided by the invention.Shown in Figure 2 is CO provided by the invention
2, SO
2, SO
3, NO
XCapture and resolving.
[specific embodiment]
The synthesis path of organometallic complex provided by the present invention; see also accompanying drawing 1: under inert gas shielding; to insert in the reaction vessel as raw material organic metal chloride II; adding the organic solvent stirring makes it to dissolve fully; add aqueous slkali then; react 0.5-24h under 0-120 ℃ environment, reaction promptly gets after finishing or promptly gets target organometallic complex I through the super-dry post processing.
CO provided by the present invention
2, SO
2, SO
3, NO
XCapture and the path of parsing, see also accompanying drawing 2: will insert in the reaction vessel as the organometallic complex II of absorbent, solvent is an organic solvent, and the concentration of organometallic complex is 0.1-10mol/L; Feed CO
2, SO
2, SO
3, NO
XIn one or more gases to be caught, pressure 0.5-10MPa; Capture temperature and be-20-120 ℃, the one way capture time is 5min-24h; After finishing, reaction promptly gets corresponding organic metal salt.After the capture process is finished, resolve 0.5-24h in 0-400 ℃ of following vacuum (0.001-0.01MPa) heating, wherein according to intensification heating-up temperature difference, the species of gases that gradient parses is different.
The present invention will be further described below in conjunction with specific embodiment:
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, R ' is a cyclohexyl, and X is an oxygen, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 90% gaseous mixture (He/CO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 25 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector then
2Concentration.Almost detect in the tail gas less than CO
2, show CO
2Capture rate near 100%, show that organo-metallic compound all changes into carbonate, organometallic complex conversion ratio and selectivity are all near 100%.After the capture process is finished, resolve 10h, CO in 150 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity be 100%, organic metal carbonate all changes into corresponding organometallic complex, absorbs repeatedly and resolves 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 2
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, R ' is a cyclohexyl, and X is an oxygen, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 90% gaseous mixture (SO
2/ CO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 45 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector then
2And SO
2Concentration.Almost detect in the tail gas less than SO
2, all be CO
2, showing that organo-metallic compound all changes into sulphite and carbonate, the organometallic complex conversion ratio is near 100%; Show SO
2Capture rate near 100%, the purifying rate of carbon dioxide is near 100%.After the capture process is finished, resolve 10h, CO in 150 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex, continues ℃ following vacuum (0.001MPa) heating of rising temperature to 250 and resolves 10h, SO
2All parse, obtain SO
2Purity near 100%, organic metal sulphite all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 3
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, R ' is a methyl, and X is an oxygen, and M is a bismuth) 10.0g, benzene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 80% gaseous mixture (CO
2/ NO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 45 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector then
2And NO
2Concentration.Almost detect in the tail gas less than NO
2, all be CO
2, show NO
2Capture rate near 100%, the purifying rate of carbon dioxide is near 100%, and organo-metallic compound all changes into carbonate and nitrate, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h in 80 ℃ of following vacuum (0.001MPa) heating, wherein according to temperature difference, NO
2All parse, obtain NO
2Purity near 100%, organic metal nitrate all changes into corresponding organometallic complex, continues ℃ following vacuum (0.001MPa) heating of rising temperature to 150 and resolves 10h, CO
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 4
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be methyl, R ' is a phenyl, and X is an oxygen, and M is an antimony) 10.0g, toluene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 50% gaseous mixture (CO
2/ SO
3), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 45 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And SO
3Concentration.Almost detect in the tail gas less than SO
3, all be CO
2, show SO
3Capture rate near 100%, CO
2Purifying rate near 100%, organo-metallic compound all changes into sulfate and carbonate, the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h in 100 ℃ of following vacuum (0.001MPa) heating, wherein according to temperature difference, CO
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex, continues ℃ following vacuum (0.001MPa) heating of rising temperature to 300 and resolves 10h, SO
3All parse, obtain SO
3Purity near 100%, organic metal sulfate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 5
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
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 an oxygen, and M is a bismuth) 10.0g, ethylene glycol 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 50% gaseous mixture (CO
2/ NO), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is-20 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2Concentration with NO.Almost detecting in the tail gas less than NO, all is CO
2, the capture rate that shows NO is near 100%, CO
2Purifying rate near 100%, organo-metallic compound all changes into nitrite and carbonate, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h in 60 ℃ of following vacuum (0.002MPa) heating, NO all parses, the purity that obtains NO is near 100%, the organic metal nitrite all changes into corresponding organometallic complex, continue ℃ following vacuum (0.001MPa) heating of rising temperature to 170 and resolve 10h, CO
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 6
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
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 a sulphur, and M is a bismuth) 10.0g, ethanol 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 50% gaseous mixture (CO
2/ NO/SO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 0 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2, SO
2Concentration with NO.Almost detect less than NO and SO in the tail gas
2, all be CO
2, show NO and SO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into sulphite and nitrite, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h in 80 ℃ of following vacuum (0.001MPa) heating, NO all parses, and the purity that obtains NO is near 100%, and the organic metal nitrite all changes into corresponding organometallic complex; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 150 and resolve 10h, do not see CO
2All parse, show that organometallic complex does not get transformed into carbonate; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 290 and resolve 10h, SO
2All parse, obtain SO
2Purity near 100%, organic metal sulphite all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 7
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4Be H, R
5, R
6, R
7, R
8Be ethyl, R ' is a phenyl, and X is a sulphur, and M is a bismuth) 10.0g, chloroform 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 50% gaseous mixture (CO
2/ NO/SO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 0 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2, SO
2Concentration with NO.Almost detect less than NO and SO in the tail gas
2, all be CO
2, show NO and SO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into sulphite and nitrite, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h in 120 ℃ of following vacuum (0.001MPa) heating, wherein according to the temperature difference, NO all parses, the purity that obtains NO is near 100%, the organic metal nitrite continues ℃ following vacuum (0.001MPa) heating of rising temperature to 250 and resolves 10h, SO all from newly changing into corresponding organometallic complex
2All parse, obtain SO
2Purity near 100%, organic metal sulphite is all from newly changing into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 8
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, be H, R
8Be phenyl, R ' is a methyl, and X is a sulphur, and M is a bismuth) 10.0g, methyl alcohol 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 60% gaseous mixture (CO
2/ SO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 0 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And SO
2Concentration.Almost detect in the tail gas less than SO
2, all be CO
2, show SO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into sulphite, shows the organometallic complex conversion ratio near 100%, selectivity 100%.After the capture process is finished, resolve 10h, wherein, do not see CO according to the temperature difference in 150 ℃ of following vacuum (0.001MPa) heating
2Parse, show that organometallic complex does not get transformed into carbonate, all change into sulphite.Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 280 and resolve 10h, SO
2All parse, obtain SO
2Purity near 100%, organic metal sulphite is all from newly changing into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 9
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, be H, R
8Be phenyl, R ' is a methyl, and X is a sulphur, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 40% gaseous mixture (CO
2/ NO
2), CO
2The pressure of gaseous mixture is 4.0MPa, and temperature is 10 ℃, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And NO
2Concentration.Almost detect in the tail gas less than NO
2, all be CO
2, show NO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into nitrate, shows the organometallic complex conversion ratio near 100%, and selectivity is near 100%.After the capture process is finished, resolve 10h, NO in 130 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain NO
2Purity near 100%, the organic metal nitrite is all from newly changing into corresponding organometallic complex; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 250 and resolve 10h, do not see CO
2Parse, show that organometallic complex does not get transformed into carbonate.Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 10
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
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 a selenium, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 50% gaseous mixture (CO
2/ SO
3), CO
2The pressure of gaseous mixture is 3.4MPa, and temperature is 20 ℃, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And SO
3Concentration.Almost detect in the tail gas less than SO
3, all be CO
2, show SO
3Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into sulfate, shows the organometallic complex conversion ratio near 100%, and selectivity is near 100%.After the capture process is finished, resolve 10h, wherein, do not see CO according to the temperature difference in 150 ℃ of following vacuum (0.001MPa) heating
2Parse, show that organometallic complex does not get transformed into carbonate, all change into sulfate.Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 300 and resolve 10h, SO
3All parse, obtain SO
3Purity near 100%, organic metal sulfate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be H, R ' is a normal-butyl, and X is an oxygen, and M is an antimony) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 40% gaseous mixture (CO
2/ SO
2), CO
2The pressure of gaseous mixture is 4.0MPa, and temperature is 10 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And NO
2Concentration.Almost detect in the tail gas less than SO
2, all be CO
2, show SO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into sulphite and carbonate, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h, CO in 150 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex, continues ℃ following vacuum (0.001MPa) heating of rising temperature to 250 and resolves 10h, SO
2All parse, obtain SO
2Purity near 100%, organic metal sulphite all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 12
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be H, R ' is a phenyl, and X is an oxygen, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 60% gaseous mixture (CO
2/ SO
2/ SO
3/ NO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 10 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2, SO
2, SO
3And NO
2Concentration.Almost detect in the tail gas less than SO
2, SO
3And NO
2, all be CO
2, show SO
2, SO
3, NO
2Capture rate near 100%, CO
2Purifying rate near 100%.Organo-metallic compound all changes into carbonate, sulphite, sulfate and nitrate, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h, NO in 60 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain NO
2Purity near 100%, organic metal nitrate all changes into corresponding organometallic complex; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 150 and resolve 10h, CO
2All parse, obtain CO
2Purity near 100%, organic metal carbonate is all from newly changing into corresponding organometallic complex; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 250 and resolve 10h, SO
2All parse, obtain SO
2Purity near 100%, organic metal sulphite all changes into corresponding organometallic complex; Continue ℃ following vacuum (0.001MPa) heating of rising temperature to 300 and resolve 10h, SO
3All parse, obtain SO
3Purity near 100%, organic metal sulfate is all from newly changing into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 13
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
4, R
5, R
6, R
8Be H, R
3, R
7Be methyl, R ' is a phenyl, and X is an oxygen, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 10% gaseous mixture (CO
2/ He), CO
2The pressure of gaseous mixture is 10.0MPa, and temperature is 10 ℃, airtight air inlet and gas outlet, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2Concentration.Almost detect in the tail gas less than CO
2, show CO
2Capture rate near 100%.CO
2All change into carbonate, show that organometallic complex captures CO
2Selectivity is near 100%.After the capture process is finished, resolve 10h, CO in 100 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 14
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
4, R
5, R
6, R
8Be H, R
3, R
7Be phenyl, R ' is a methyl, and X is an oxygen, and M is an antimony) 10.0g, chloroform 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 40% gaseous mixture (CO
2/ O
2), CO
2The pressure of gaseous mixture is 10.0MPa, and temperature is 120 ℃, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And O
2Concentration.Almost detect in the tail gas less than CO
2, all be O
2, show CO
2Capture rate near 100%, O
2Purifying rate near 100%.Organo-metallic compound all changes into carbonate, shows that the organometallic complex conversion ratio is near 100%.After the capture process is finished, resolve 10h, CO in 100 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity near 100%, organic metal carbonate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
Embodiment 15
In being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet, add organometallic complex I (R successively
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be H, R ' is a normal-butyl, and X is an oxygen, and M is a bismuth) 10.0g, carrene 5mL, sealed reactor feeds CO behind the stirring 5min
2Concentration is 10% gaseous mixture (CO
2/ O
2/ N
2), CO
2The pressure of gaseous mixture is 10.0MPa, and temperature is 50 ℃, and stirring reaction 1h utilizes CO in the gas chromatograph detection of dynamic tail gas that has thermal conductivity cell detector
2And O
2Concentration.Almost detect in the tail gas less than CO
2, all be N
2And O
2, CO
2All change into carbonate, show CO
2Conversion ratio is near 100%, CO
2Capture rate near 100%.After the capture process is finished, resolve 10h, CO in 100 ℃ of following vacuum (0.001MPa) heating
2All parse, obtain CO
2Purity near 100%, CO
2Purifying rate near 100%, organic metal carbonate all changes into corresponding organometallic complex; Absorb repeatedly and resolve 10 times, the structure of organometallic complex is not destroyed, and absorbs and not decline of analytic ability.
In order to further specify the superiority of the inventive method, select following absorption system for use as a comparison case.
Comparative example 1
Add MEA 10.0g, carrene 5mL in being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet successively, sealed reactor feeds CO behind the stirring 5min
2Concentration is 40% gaseous mixture (CO
2/ SO
2/ SO
3/ NO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 20 ℃, stirring reaction 1h.Utilization has CO in the gas chromatograph detection of dynamic tail gas of thermal conductivity cell detector
2, SO
2, SO
3And NO
2Concentration.Detect SO in the tail gas
2, SO
3, NO
2And CO
2, show the poor selectivity of MEA, CO
2Purifying rate near 73%.In addition, because the existence of highly acid gas is arranged, variation has taken place in the structure of absorbent, and the energy consumption of regeneration significantly rises, and amine degradation has taken place part simultaneously.
Comparative example 2
Add 2-(dimethylamino)-ethanol (DEAE) 10.0g, carrene 5mL in being furnished with the 100mL stainless steel cauldron of air inlet and gas outlet successively, sealed reactor feeds CO behind the stirring 5min
2Concentration is 40% gaseous mixture (CO
2/ SO
2/ SO
3/ NO
2), CO
2The pressure of gaseous mixture is 3.0MPa, and temperature is 20 ℃, stirring reaction 1h.Utilization has CO in the gas chromatograph detection of dynamic tail gas of thermal conductivity cell detector
2, SO
2, SO
3And NO
2Concentration.Detect SO in the tail gas
2, SO
3, NO
2And CO
2, show the poor selectivity of MEA, CO
2Purifying rate near 83%; In addition, because the existence of highly acid gas is arranged, variation has taken place in the structure of absorbent, and the energy consumption of regeneration significantly rises, and amine degradation has taken place part simultaneously.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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 (10)
1. a capture, fixing and purification of carbon dioxide (CO
2), sulfur dioxide (SO
2), sulfur trioxide (SO
3) and nitrogen oxide (NO
X) chemical method, it is characterized in that this chemical method adopts organo-metallic compound and solvent as catching and chemical fixatives.
2. method according to claim 1 is characterized in that, described organo-metallic compound is organo-bismuth complex and the organic stibium complex with structural formula I:
Wherein, such complex is the novel organometallic complex that contains bridge nitrogen atom ligand of a class, and 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)], R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be substituting group identical or inequality on the phenyl ring; R ' is the substituting group on the nitrogen-atoms; Metal center (M
3+) be bismuth (Bi
3+) and antimony (Sb
3+); M
3+With M
3+Be to link to each other by oxygen group elements; And in such complex, M
3+Except that with part in two carbon atoms form the covalent bonds, also with part in nitrogen-atoms form coordinate bond, with M
3+Form covalent bond with the chalcogen atom.
3. synthetic method according to claim 3 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 for alkyl (C0-C20) or aryl (C6-C20) identical or inequality and have different heteroatomic various substituted radicals, wherein preferred H, methyl, ethyl, the tert-butyl group, cyclohexyl, phenyl or naphthyl; Described oxygen group elements be oxygen, sulphur, selenium and tellurium (O, S, Se, Te), wherein preferred oxygen and sulphur.
4. method according to claim 1 is characterized in that, described organo-metallic compound is to react in organic solvent and water by organic metal chloride and corresponding alkali to make; Its reaction condition is under the inert gas shielding, reaction temperature 0-120 ℃, and reaction time 0.5-24h.
5. method according to claim 4 is characterized in that, described alkali is inorganic base and alkaline, inorganic salts; Wherein, the preferred lithium hydroxide of inorganic base, NaOH, potassium hydroxide, cesium hydroxide; Alkalescence inorganic base alkali metal salt, wherein preferred vulcanized sodium, potassium sulfide, sodium selenide, potassium selenide, tellurium sodium, tellurium potassium, sodium carbonate, sodium acid carbonate, potash, saleratus, cesium carbonate; Described organic solvent is polarity and non-polar solven, wherein preferred carrene, chloroform, benzene, toluene; Described inert gas preferred nitrogen and argon gas.
6. method according to claim 1 is characterized in that described method can absorb CO
2, SO
2, SO
3, NO
XIn the gas one or more are preferentially caught acid stronger species of gases under the same conditions.
7. according to claim 1 and 6 described methods, it is characterized in that described method can parse by the gas that the change condition will be caught and fix, and can under different temperatures, realize the gradient parsing.
8. method according to claim 1 is characterized in that, described catch with the chemical fixation condition be that the concentration of organometallic complex is 0.1-10mol/L; Solvent is an organic solvent, gas pressure 0.5-10MPa, and temperature is-20-120 ℃, the one way capture time is 5min-24h.
9. according to claim 1 and 8 described methods, it is characterized in that described organic solvent is organic polar solvent and non-polar solven, wherein preferred toluene, carrene, methyl alcohol, ethanol, ethylene glycol.
10. according to claim 1 and 7 described methods, it is characterized in that the condition of described parsing is: resolve 0.5-24h in 0-400 ℃ of following vacuum (0.001-0.01MPa) heating.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775378A (en) * | 2011-12-20 | 2012-11-14 | 湖南大学 | Solvent-free catalytic synthesis method of cyclic carbonate |
| CN102921273A (en) * | 2012-11-05 | 2013-02-13 | 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 |
| CN103845998A (en) * | 2012-11-30 | 2014-06-11 | 阿尔斯通技术有限公司 | Post absorber scrubbing of so3 |
| CN105214457A (en) * | 2014-06-05 | 2016-01-06 | 魏雄辉 | A kind of fume desulfuring and denitrifying Processes and apparatus |
| CN113348030A (en) * | 2019-01-28 | 2021-09-03 | 乔治·罗伯特·理查森 | CO2、NOxAnd SO2Chemical sealing of |
| CN113891758A (en) * | 2019-05-28 | 2022-01-04 | 株式会社神户制钢所 | Gas processing method and gas processing apparatus |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775378A (en) * | 2011-12-20 | 2012-11-14 | 湖南大学 | Solvent-free catalytic synthesis method of cyclic carbonate |
| CN102775378B (en) * | 2011-12-20 | 2015-10-28 | 湖南大学 | A kind of solvent-free process for catalytic synthesis of cyclic carbonate |
| CN102921273A (en) * | 2012-11-05 | 2013-02-13 | 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 |
| CN103845998A (en) * | 2012-11-30 | 2014-06-11 | 阿尔斯通技术有限公司 | Post absorber scrubbing of so3 |
| CN103845998B (en) * | 2012-11-30 | 2016-05-25 | 阿尔斯通技术有限公司 | The rear absorber scrubbing of sulfur trioxide |
| CN105214457A (en) * | 2014-06-05 | 2016-01-06 | 魏雄辉 | A kind of fume desulfuring and denitrifying Processes and apparatus |
| CN105214457B (en) * | 2014-06-05 | 2018-04-17 | 魏雄辉 | A kind of fume desulfuring and denitrifying Processes and apparatus |
| CN113348030A (en) * | 2019-01-28 | 2021-09-03 | 乔治·罗伯特·理查森 | CO2、NOxAnd SO2Chemical sealing of |
| CN113891758A (en) * | 2019-05-28 | 2022-01-04 | 株式会社神户制钢所 | Gas processing method and gas processing apparatus |
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| CN102091503B (en) | 2015-10-07 |
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