CN1111435C - Reductive Decomposition Method of Chemical Pollutants - Google Patents
Reductive Decomposition Method of Chemical Pollutants Download PDFInfo
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- CN1111435C CN1111435C CN93104546A CN93104546A CN1111435C CN 1111435 C CN1111435 C CN 1111435C CN 93104546 A CN93104546 A CN 93104546A CN 93104546 A CN93104546 A CN 93104546A CN 1111435 C CN1111435 C CN 1111435C
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- 238000000034 method Methods 0.000 title claims abstract description 98
- 239000000126 substance Substances 0.000 title claims abstract description 64
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 25
- 230000002829 reductive effect Effects 0.000 title claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 title claims description 44
- 231100000719 pollutant Toxicity 0.000 title claims description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 35
- -1 free radical hydrogen ions Chemical class 0.000 claims abstract description 28
- 150000002894 organic compounds Chemical group 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 24
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000000356 contaminant Substances 0.000 claims abstract 10
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract 2
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
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- 150000001412 amines Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229940100198 alkylating agent Drugs 0.000 claims 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
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- 150000004665 fatty acids Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 description 2
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- 238000001311 chemical methods and process Methods 0.000 description 2
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- 150000004678 hydrides Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 231100001240 inorganic pollutant Toxicity 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
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- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
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- 238000002203 pretreatment Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
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- 239000004317 sodium nitrate Substances 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- Fire-Extinguishing Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A process for the reductive decomposition of a chemical contaminant comprising reacting at least one alkali or alkaline earth metal compound with the chemical contaminant to form a reaction mixture, wherein the reaction mixture further comprises a hydrogen donor compound and a catalyst to promote the formation of free radical hydrogen ions. These methods also include heating the reaction mixture to a predetermined temperature for a time sufficient to promote the generation of free radical hydrogen ions therein and the reductive decomposition of the chemical contaminants. The process is useful for the reductive decomposition of organic and inorganic compounds.
Description
The present invention relates to the reductibility decomposition method of the base catalysis of chemical pollutant.More specifically say, the present invention relates to produce in the presence of the free hydrogen ionic catalyzer, organic and/or mineral compound are carried out the method for destructive decomposition with basic metal and/or alkaline earth metal compound and hydrogen donor.
As everyone knows, the organic compound of various synthetic fontanelizations and many mineral compound can work the mischief to public health and environment.Polychlorobiphenyl (PCB class), dibenzo two oxines, diphenylene-oxide, dichloro phenylbenzene trichloromethane (DDT), Dieldrin-attapulgite mixture, Tri-6 and Niran and other fontanel agricultural chemicals, found it is the material of persistent murder by poisoning environment, they require to have safe and effective treatment process.The PCB compounds has proposed the handling problem of especially severe.Because their good insulating property are widely used in electric installation such as transformer and the electrical condenser etc. in the past as the dielectric fluid additive.The application in many aspects of PCB compounds is prohibited by EPA, and this is because they are stored and high toxicity in the intravital accumulation of people.Therefore, need remove and/or destroy the method for fontanel organic compound such as PCB compounds.
Many non-fontanelizations are organic has also known it is to the environment toxic substance with mineral compound, also needs safe and effective processing means.These compounds comprise nitrogenous compound, and P contained compound, oxygenatedchemicals and sulfocompound etc. comprise organic and inorganic.
Many destructions or the method for decomposing the fontanel organic compound have been known in this area.For example, the United States Patent (USP) 4,447,541 and 4,574 of Peterson, 013 discloses the method for removing by the pollution of the soil of fontanel orgnic compound pollution.United States Patent (USP) 4,447,541 disclosed a kind of methods of Peterson are with the mix reagent of basic component and a kind of sulfoxide catalyst (DMSO) and by PCB compounds Contaminated soil thorough mixing.This mix reagent makes the fontanel pollutent from the soil desorption, thereby makes pollutent take off fontanelization.Yet, the shortcoming of this method is that its kinetics is slow relatively, thereby make PCB concentration be reduced to acceptable level several very long like this cycles of thoughtful some months of needs, destroy the pollutent generation in order to make, soil should complete drying, need a large amount of reagent, and sulfoxide catalyst might make pollutants transfer before pollutent is destroyed.United States Patent (USP) 4,574,013 disclosed method of Peterson is the warm sludge slurry with the mixture process contaminated soil of basic component and sulfoxide catalyst.Yet this method has the shortcoming similar to last method, and sulfoxide catalyst may make pollutants transfer arrive uncontaminated system, and sulfoxide catalyst produces malodorous compounds when being heated to high temperature, and resolves into flammable by product under the higher temperatures condition.
People's such as Rogers United States Patent (USP) 4,675,464 discloses a kind of chemical process for destroying of fontanel aliphatic hydrocrbon, more specifically the chemical process for destroying of ethylidene perbromide.Alkali metal hydroxide is dissolved in 1,2 ethylene glycol, again with products therefrom and fontanel hydrocarbon reaction.People such as Rogers also disclose temperature of reaction should remain on 30 ℃ or following, so that reaction product remains in the solution.
People's such as Rogers United States Patent (USP) 5,019,175 discloses a kind of destruction methods of the fontanel organic compound in pollution medium, and wherein a kind of aqueous solution that contains about 0.1 to 20 weight % polyoxyethylene glycol is added in a kind of polluted medium.Also a kind of alkali metal hydroxide is added in this pollution medium, this pollution medium for some time of heating under a certain temperature, make medium be enough to dehydration.Again medium is further heated for some time between about 100-350 ℃, make the fontanel organic compound be enough to effectively be destroyed, in medium, add a kind of acid, present in an amount at least sufficient to make the pH of medium to become about 9 from about 7.
People's such as Rogers United States Patent (USP) 5,039,350 disclose the decomposition method of the fontanel organic compound that is contained in a kind of pollution medium, comprising add a kind of alkaline carbonate or supercarbonate in this pollution medium, medium are heated between about 250-400 ℃.
People's such as Rogers United States Patent (USP) 5,064,526 discloses a kind of fontanelization in a kind of pollution substance or decomposition method of non-fontanel organic pollutant of being contained in.This method comprises a kind of basic metal of adding or alkaline earth metal carbonate, supercarbonate or oxyhydroxide in contaminated material, has wherein also added hydrogen donor compound and carbon compound as catalyzer.This material is heated to dehydration, further is heated to 200-400 ℃ again, cause to form the radical hydrogen ion to realize decomposition.Adding a kind of acid to this material makes pH reach 7-9.
People's such as Pytlewski United States Patent (USP) 4,400,552 discloses a kind of method of decomposing the fontanel organic compound, comprising using a kind of alkali metal hydroxide and the reaction product of polyoxyethylene glycol or polyalkylene glycol monoalkyl ether and reagent of oxygen of comprising.People's such as Pytlewski United States Patent (USP) 4,337,368 and 4,602,994 disclose the organic similarity method of decomposition fontanelization.The United States Patent (USP) 4,430,208,4,417,977,4,460 of pytlewski in addition, 797 and 4,471,143 also disclose organic separation of fontanelization and/or decomposition method.Yet the shortcoming of these methods is to need to use excess base metal hydroxides and polyethylene glycol reagents, so that it is at whole pending pollutent, as the uniform distribution of inner acquisition such as soil, settling, mud.People's such as Pytlewski United States Patent (USP) 4,349,380 and 4,523,043 metal and the polyoxyethylene glycol of decomposition organosulfur compound or the use of the reagent that polyalkylene glycol monoalkyl ether is made that discloses by basic metal or alkaline earth metal hydroxides and be used for removing the containing metal material.Similarly, the United States Patent (USP) 4,351,718 and 4,353,793 of Brunelle discloses the method for removing many chimneyization hydrocarbon from the solution of non-polar organic solvent, comprising the solution with the mixture process pollutent of a kind of polyoxyethylene glycol and alkali metal hydroxide.The similar shortcoming of these methods is to need excessive reagent, can not realize complete dechlorination and/or even realize that the part dechlorination all needs the too much time.
Remove and/or destroy other method that is contained in the fontanel organic compound in the pollution substance, also be disclosed in people's such as Howard United States Patent (USP) 4,327,027, the U.S.P.4 of Heller, 483,716, people's such as Mendiratta U.S.P.4,663,027, people's such as Meenan U.S.P.4,685,220 and 4,793,937, people's such as Rossi U.S.P.4,761,221, people's such as Zeff U.S.P.4,792,407, european patent application 118,858, chemical abstracts V.82, people such as 139620P (1975) and Kornel are at Journal of Hazardous Materials, 12 (1985) PP.161-176.Yet, these and other method that is used for removing and/or destroy at the fontanel organic compound of pollution medium is not enough in this area, because for reach acceptable remove and/or the horizontal required time of destructive long, the usage quantity of all ingredients is excessive, the reagent costliness of using, toxicity and/or flammable production of by-products, and/or can not obtain required removing and/or the destruction level.
Thereby, be necessary to improve the method for reducing of chemical pollutant, make cost reduce and overcome the shortcoming of prior art.
Therefore, an object of the present invention is to provide the novel method that reductibility is decomposed the chemical pollutant that includes organic compounds and/or mineral compound, these pollutents can or be contained in the pollution medium with pure form Individual existence.The method that another purpose of the present invention is to provide the reductibility of chemical pollutant to decompose, these methods are used at least a hydrogen donor compound.Another object of the present invention is to provide application greatly to reduce, subtract the decomposition method of the lower-cost chemical pollutant of agent than prior art amount of reagent.Another purpose of the present invention is to provide the method that reaches environmentally acceptable chemical pollution compound level.Relevant purpose of the present invention provides the method that obtains environmentally acceptable pollutant level at short notice.
These purposes and other purpose realize by method of the present invention, relate in the inventive method pure form or be contained in the fontanelization in the pollution medium and/or the base catalysis decomposition of non-fontanel organic compound and/or mineral compound.The inventive method comprises makes at least a basic metal or alkaline earth metal compound and chemical pollutant chemical combination form a kind of reaction mixture, and wherein this reaction mixture also contains a kind of hydrogen donor compound and the catalyzer that impels the radical hydrogen ion to form.These methods also comprise this reaction mixture in certain predetermined temperature range, and heating is enough to cause that wherein radical hydrogen ion forms and effective time of reductibility chemical decomposition pollutent.I in addition) be a kind of organic compound when chemistry dyes thing, when basic metal or alkaline earth metal compound combine with chemical pollutant, predetermined temperature range for from about 50 ℃ to being lower than 200 ℃, ii) working as chemical pollutant is a kind of organic compound, when alkali metal compound and alkaline earth metal compound all combine with chemical pollutant, predetermined temperature range is that predetermined temperature range is from about 50 ℃ to 400 ℃ from about 50 ℃ to 400 ℃ and iii) when chemical pollutant is a kind of mineral compound.
After adding the reaction mixture of thermal pollution, catalyzer causes from hydrogen donor compound formation radical hydrogen ion.This radical hydrogen thereby produced in the original place promptly produces in identical processed reaction mixture, and chemical pollutant is played reductive agent.The organic pollutant that is reduced resolves into simple hydrocarbon structure.The decomposition of fontanelization and non-fontanel organic chemical pollutant along with temperature raises, is more depended on the easy degree that is provided hydrogen by donor compound (being promoted by catalyzer) in pre-determined range.Mineral compound produces the wherein reduction form of institute's containing metal through reduction, and/or hydride etc.
After following detailed description, the easier understanding that will become of these and other objects and advantage.
The present invention includes method pure or that be contained in the chemical pollution compound reductibility decomposition in the pollution medium.The medium that pollutes can comprise soil, settling, mud or a kind of liquid.Present method is specially adapted to soil, settling and mud.Present method is applicable to and contains up to 100, the chemical pollutant of 000ppm, organic compound as fontanelization, aliphatic or aromatics, as the PCB class, or even the medium of more high-load fontanel organic compound, and be applicable to and contain up to 100 the non-fontanel organic pollutant of 000ppm or the medium of inorganic pollutant.Pollutant levels can be handled by method of the present invention during 000ppm greater than 100, and the add-on of promptly regulating basic metal or alkaline earth metal compound is in case discharge the potential pollutent in the excessive rising of temperature and the technology.The medium that is applicable to pollution of the present invention also can comprise absorption agent or sorbent material, as exhausted activated carbon etc.
The chemical pollutant of handling by present method can comprise a kind of organic compound or a kind of mineral compound.The non-aromatic compound that can comprise the aromatic substance and the fontanelization of fontanelization by the organic chemical pollutant that present method is handled includes but not limited to PCB class, PCP, chlorofluorocarbon, aliphatic series, ring and heterogeneous ring compound.Other organic pollutant can comprise nitrogenous compound, and wherein reductibility is decomposed meeting generation amine and/or ammonia.As is generally known the further reduction decomposition of amine can cause complete denitrogenation and produce ammonia.Reductibility of the present invention is decomposed and be can be used for sulfocompound, both of organic or inorganic.Sulfocompound decomposes generation sulfide and/or elementary sulfur usually.Organophosphorus and inorganic phosphorous compound also can be handled by method of the present invention, as the result that reductibility is decomposed, produce the reduction form of phosphine or other phosphorus.If desired, can realize dephosphorylation completely.Oxygenatedchemicals, inorganic and organic both, also can handle by present method, decompose to produce the oxygen-free compound of water and lower molecular weight through reductibility.The example of organic oxygen-containing thing comprises octanol, polyoxyethylene glycol, contains methoxyl group aromatic substance etc.Generally, when handling mineral compound by reductibility decomposition method of the present invention, the metallic compound of their reduction forms in the middle of reduction produces comprises hydride etc.
Usually, present method comprises basic metal and/or alkaline earth metal compound, as a kind of carbonate, supercarbonate, oxide compound or oxyhydroxide, maybe can produce the compound of a kind of carbonate, supercarbonate, oxide compound or oxyhydroxide, be added in the pure chemistry pollutent or be added in the pollution medium that contains one or more chemical pollution compounds.This basic metal or alkaline earth metal compound, as carbonate, supercarbonate, oxide compound or oxyhydroxide, can the aqueous solution or be added among pure pollutent or the pollution medium with the form of high boiling solvent.Another kind of mode, basic metal or alkaline earth metal compound can solids suspension or the form of dispersion liquid be added in the pollutent.When basic metal or alkaline earth metal compound add fashionablely with the form of the aqueous solution or high boiling solvent, water in the aqueous solution or solvent help this metallic compound to be evenly distributed on pollutent or pollution medium everywhere.If basic metal or alkaline earth metal compound add with the high boiling solvent form, the boiling point of suitable solvent is at least 100 ℃, preferred about 200 ° to about 500 ℃.Preferred solvent comprises hydrocarbon compound.In a preferred additional embodiment, basic metal and alkaline-earth metal can aqueous solution form be added in the pollution medium, and wherein the aqueous solution also comprises a kind of high boiling solvent.
This basic metal or alkaline earth metal compound, the mol ratio that combines with chemical pollutant as a kind of carbonate, supercarbonate, oxide compound or oxyhydroxide is about 1: 1 to about 10: 1.The concrete amount of required basic metal or alkaline earth metal compound depends on the amount of the pollutent that is decomposed.Any basic metal or alkaline-earth metal or its mixture all can be used for the present invention.Preferred basic metal comprises that lithium, sodium and potassium serve as special preferred with sodium and potassium.
Basic metal and alkaline earth metal carbonate, supercarbonate and oxide compound are preferred when using in some system, and these are owing to compare with basic metal or alkaline earth metal hydroxides, and their corrodibility is lower.Yet, when pollution medium is acid or comprises a kind of hydrocarbons, preferably use the oxyhydroxide or the oxide compound of basic metal or alkaline-earth metal.
In one embodiment, in the method that chemical pollutant reductibility of the present invention is decomposed, alkali metal compound is used in combination with alkaline earth metal compound.More particularly, preferably with the reaction of alkali metal compound starting decomposition.Yet alkali metal compound is more expensive than alkaline earth metal compound.For example, the cost of many alkaline earth metal compounds is 1/5 of a corresponding alkali metal compound.Therefore, alkaline earth metal compound as alkaline earth metal oxide, can be used for the negatively charged ion that combines and disengage with chemical pollutant to provide with alkali metal compound, the halogen ion that in reductibility is destroyed, disengages of halogenated compound for example, the positively charged ion of the stoichiometry amount of reaction.When basic metal and alkaline earth metal compound were used in combination, alkaline earth metal compound is inherent and the water that forms in chemical reaction in the absorption reaction mixture also.Therefore, in the method, can use the alkali metal compound of more a spot of costliness to be used in combination with alkaline earth metal compound.As a result, this reductibility being decomposed can be at lesser temps, more carry out under rapid rate and the lower raw materials cost.This embodiment is particularly preferred for handling organic compound.
According to an important feature of the present invention, pollute impurity and also contain a kind of hydrogen donor compound.This hydrogen donor compound can be provided for the hydrogen ion with the chemical pollutant reaction.This hydrogen donor compound can include organic compounds, and polymkeric substance, or a kind of gas as hydrogen, can be contained in the medium of pollution with chemical pollutant originally.If pending pollutent or the not hydrogeneous donor compound of pollution medium, the hydrogen donor compound can be added in pollutent or the pollution medium with basic metal or alkaline earth metal compound.In one embodiment, this hydrogen donor compound can comprise a kind of high boiling point polarity or non-polar solvent, as adding the solvent of basic metal or alkaline earth metal compound.Suitable hydrogen donor compound comprises lipid acid, Fatty Alcohol(C12-C14 and C12-C18) or hydro carbons, amine etc.In one embodiment, this hydrogen donor compound can be modified, and disengage this hydrogen ion so that realization is easier, thereby the inventive method can be carried out under lower temperature.For example, the hydrogen donor compound can be handled with a kind of alkylating reagent, is created in the three generations's hydrogen atom in the hydrogen donor compound of modification.This three generations's hydrogen atom disengages the formation hydrogen ion easily, thereby method can be carried out under lower temperature.
In order to activate the hydrogen donor compound, must add catalyzer, the preferably form in solution or in the suspension to produce the radical hydrogen ion.A kind of inexpensive catalyzer comprises a kind of carbon source.One of carbon source can be water-soluble and be suitable for the example that the present invention uses and comprise carbohydrate, as sucrose.Another is applicable to that the example of carbon source of the present invention comprises that carbon black or other have the carbon source of large surface area.In an alternative embodiment, catalyzer comprise a kind of phase catalyst, as polyalkylene glycol, as polyoxyethylene glycol.In the third embodiment, catalyzer can comprise the combination of carbon source and phase catalyst, as polyoxyethylene glycol.Catalyst for application is to be enough to that the amount that required reductibility decomposition takes place chemical pollutant is existed in the inventive method.
One forms when also containing a kind of organic hydrogen donor compound and a kind of reaction mixture that is used to form the hydrionic catalyzer of radical when basic metal and/or alkaline earth metal compound combine with chemical pollutant, heats this reaction mixture.Specifically, will heat under reaction mixture certain temperature in a pre-determined range, be enough to heat-up time make radical hydrogen ion wherein to form, and chemical pollutant generation reductibility is decomposed.Heating steps can carry out under normal atmosphere or buck or boost as required.The reductibility of chemical pollutant is decomposed required time, depends on concrete pollutent and concentration thereof.Usually, about 0.5-2 hour enough.
Predetermined temperature range is about 50 °-Yue 400 ℃, depends on pending chemical pollutant and used basic metal and/or alkaline earth metal compound.When chemical pollutant is a kind of organic compound, basic metal or alkaline earth metal compound therewith chemical pollutant in conjunction with the time, the preferably about 50-of predetermined temperature range is lower than 200 ℃.When chemical pollutant is a kind of organic compound, basic metal or alkaline earth metal compound both be used for therewith chemical pollutant in conjunction with the time, predetermined temperature range is about 50 °-Yue 400 ℃.If working as this chemical pollutant is mineral compound, predetermined temperature range is about 50 ℃-400 ℃.Usually,, for example contain fluorochlorohydrocarbon for non-aromatic compound, fontanel solvent and ring compound take off fontanelization or dehydrogenation can carried out up to being lower than under 200 ℃.On the other hand, the fontanel that takes off for aromatic substance needs 150 °-400 ℃.To a kind of special chemical pollutant, can use lesser temps, method is to use a kind of alkylating reagent, aluminum compound, phosphoric acid etc. carry out pre-treatment to the hydrogen donor compound as discussed earlier.
When the reaction mixture that contains chemical pollutant was heated, catalyzer as a kind of carbon source (being carbon black or carbohydrate, as sucrose), can form the active hydrogen ion from the hydrogen donor compound.This catalyzed reaction can be represented by following reaction formula:
Wherein R is the hydrogen donor compound, and M is a metallic compound, and carbon * is a carbon source, for example a kind of carbohydrate, H
*It is the radical hydrogen ion.This activity radical hydrogen ion then with chemical pollutant, for example a kind of chimney organic pollutant is pressed following formula and is answered:
Wherein R-X is the fontanel organic pollutant, and X is a fontanelle atom, and R-H is the reduction form of pollution compound.
Therefore, basic metal and alkaline earth metal compound catalysis take off the reductive action of fontanel effect and fontanelization and non-fontanel pollutent.
At last, when handling pollution medium, this medium is further handled in also available a kind of acid.The amount that adds acid is preferably that to be enough to provide the pH value to medium be about 7 to about 9.The acid that is fit to use in the present invention comprises sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid.Outside the demineralizing acid, these acid are neutralization medium not only, and valuable soil and fertilizer also is provided, as the Na from using sulfuric acid to obtain
2SO
4Or sodium sulfate, from the NaH that uses phosphoric acid to obtain
2PO
4, Na
2HPO
4, Na
3PO
4Or sodium phosphate, and NaNO from using nitric acid to obtain
3Or SODIUMNITRATE, when being used as basic metal as if sodium.If use potassium, then generate sylvite.If the medium that need obtain then can be by safe transfer in its original environment.
In the replacement embodiment of the inventive method, the chemical pollutant that can extract from pollution medium is collected with enriched material, is extracted in the high boiling point oil again.Pollutent then can be by using the inventive method to destroy, and wherein basic metal and/or alkaline earth metal compound, hydrogen donor compound and catalyzer are added in the pollutent, heat the mixture that obtains in a manner described.
Usually, oxygen is for method of the present invention and harmless, so air need not to get rid of.When being used for the depolluting of hydrocarbon fluid aliphatic hydrocrbon or aromatic hydrocarbons, excluding air may be needed in case the burning of hydrocarbon.Therefore present method can implemented in the presence of the oxygen-containing atmosphere or under lacking.
Because present method is used basic metal or alkaline earth metal compound in a small amount, also have solvent as needs, be used for utilizing again so need not to reclaim excess reagent.Yet because the present invention can use medium and distribution basic metal or alkaline earth metal compound wherein that water-wet is polluted, the cost of present method greatly reduces than the cost of the prior art method of using polyoxyethylene glycol wetting removal medium.Present method can be one continuously or in the batch systems, if need, institute can carry out in a simple reaction device in steps.
And, the decomposition method of base catalysis of the present invention is more excellent than the prior art method of using the reagent that obtains from the reaction of alkali metal hydroxide and polyoxyethylene glycol, the decomposition of fontanelization and non-fontanel organic contamination compound, but reach more high-grade degree within a short period of time.Another advantage that the inventive method is compared with the prior art method is that also the prior art method can not effectively decompose and remove the organic and inorganic pollutant of non-fontanelization from pollution medium.
Also obviously, the product of the inventive method can be used for preparing compound in other application, thereby the inventive method can be looked at as the method for synthetic these compounds.
Method of the present invention is demonstrated in following example:
Example 1
The reductibility of this example demonstration organic compounds containing sulfur is decomposed.Particularly, in a 250ml Florence flask, make 50ml hydrocarbon solvent (boiling point 100-400 ℃), the 0.1g C catalyst, 0.10mol dimethyl sulfoxide (DMSO) (DMSO) and 0.3mol sodium hydroxide react.With magnetic splash bar stirred reaction mixture, flask places on the hot plate heating and is connected with water condenser.Reaction mixture is heated to 50 °-100 ℃.As a result, DMSO decomposes generation sodium sulphite, and its amount equals with the sulfur content in the DMSO introducing flask.In addition, the volatile constituent of collecting in the reaction period is the methane that the methyl group reduction of DMSO produces after measured.Organic can being decomposed by similar step with inorganic sulphide produces sulfide and elementary sulfur.Nitrogenous, phosphorous and oxygen containing compound also can be by this method, and reductibility is decomposed in 50 ℃-Yue 300 ℃ temperature range.
Example 2
The reductibility of the non-aromatics chloro-hydrocarbons of this example demonstration is decomposed the i.e. fontanel effect of taking off of 1.In the 250ml Florence flask, put into the petroleum naphtha of the high fragrance of 100ml, 0.01g contains the phase catalyst of polyoxyethylene glycol (molecular weight 60-1000), and 1.0g 1 and 2.0g sodium hydroxide make it to react.Reaction medium is risen to about 100 ℃ from room temperature, make it complete dechlorination.In the embodiment of a replacement, the catalyzer of carbonaceous sources is used for replacing or using with the polyoxyethylene glycol phase catalyst.This phase catalyst does not consume in reaction, can repeat this treating processes not adding under the catalyzer situation.Use this method that nitrogenous, sulfur-bearing, phosphorous and oxygenatedchemicals reductibility are decomposed.
Example 3
The reductibility that the demonstration of this example uses the combination of basic metal and alkaline earth metal compound to contain the fontanel aromatic substance is decomposed.In the 250ml Florence flask, add 100ml varsol (100 °-350 ℃ of boiling points), 0.3M pentachlorophenol (PCP), 0.3M sodium hydroxide, 0.3M calcium oxide and 0.1g C catalyst make it to react.Reaction medium is heated to 150 ℃ of-350 ℃ of temperature, to realize the complete dechlorination of pentachlorophenol.When being used in combination C catalyst and phase catalyst, taking off the fontanel reaction and can further improve.
Therefore, to destroy aspect the organic compound of fontanelization and non-fontanelization and the mineral compound in reductibility be favourable to the inventive method.The inventive method is used inexpensive relatively compound, i.e. basic metal or alkaline earth metal compound, and as carbonate, supercarbonate, oxide compound and oxyhydroxide, the high boiling hydrocarbon solvent is hydrogen donor compound and a kind of or C catalyst of obtaining prefabricated by carbohydrate.Compare with the method for prior art, the amount of reagent that the present invention uses is less.In addition, the corrodibility of basic metal of using among the present invention or alkaline earth metal carbonate, supercarbonate and oxide compound is less than the oxyhydroxide of basic metal of using in the prior art and alkaline-earth metal, although need sometimes or preferred these oxyhydroxide.Therefore, method of the present invention provides a kind of chemical pollution compound that makes to destroy or revert to improving one's methods of the level of can't check.The organic products that is produced by present method is the material of simple lower molecular weight, for example hydro carbons, alkanes, alcohols etc., and they are the non-changes, non-deforming and atoxic that causes to biology.
Above-mentioned example is used to demonstrate specific embodiments of the present invention, is not the scope of planning to limit the inventive method.The one of ordinary skilled in the art also understands other embodiment and advantage in the invention scope of request patent protection.
Claims (14)
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| US4400552A (en) * | 1980-04-21 | 1983-08-23 | The Franklin Institute | Method for decomposition of halogenated organic compounds |
| US5064526A (en) * | 1990-04-27 | 1991-11-12 | The United States Of America As Represented By The Administrator Of The Environmental Protection Agency | Method for the base-catalyzed decomposition of halogenated and non-halogenated organic compounds in a contaminated medium |
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| US4400552A (en) * | 1980-04-21 | 1983-08-23 | The Franklin Institute | Method for decomposition of halogenated organic compounds |
| US5064526A (en) * | 1990-04-27 | 1991-11-12 | The United States Of America As Represented By The Administrator Of The Environmental Protection Agency | Method for the base-catalyzed decomposition of halogenated and non-halogenated organic compounds in a contaminated medium |
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