CN1302834C - Method for dechloridizing organochloric compound - Google Patents

Method for dechloridizing organochloric compound Download PDF

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CN1302834C
CN1302834C CNB2003101029418A CN200310102941A CN1302834C CN 1302834 C CN1302834 C CN 1302834C CN B2003101029418 A CNB2003101029418 A CN B2003101029418A CN 200310102941 A CN200310102941 A CN 200310102941A CN 1302834 C CN1302834 C CN 1302834C
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dechlorination
reaction
antichlor
cao
compound
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CN1539693A (en
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郑明辉
马小东
刘文彬
张兵
赵兴茹
钱永
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The present invention provides a method for dechlorinating organic chlorine compounds, which comprises the following steps: a mixture of calcium oxide (CaO) and iron oxide (Fe2O3) or a composite oxide of calcium and iron is used as a dechlorinating agent, and the dechlorinating agent is sufficiently evenly mixed with hexachlorobezene which is a representative substance in an organic chlorine compound in a sealed container and reacts with the hexachlorobezene at the temperature of higher than 200DEG C so as to dechlorinate the hexachlorobezene. The method is also suitable for processing other organic chlorine compounds, such as polychlorinated biphenyl (PCB), DDT, etc.

Description

A kind of method to the organochlorine compound dechlorination
Technical field
The present invention relates to a kind of method to the organochlorine compound dechlorination.
Background technology
Organochlorine compound (chlorinated organic compounds) is the important compound of a class, is widely used for various chemical raw materials, reagent.
In numerous organochlorine compounds, there are some compounds not only to have higher toxicity, and in environment, are difficult to degraded, ecological environment and health are constituted a threat to.What people paid close attention to the most is the potential harm of persistence organic pollutant that is difficult to degrade.Wherein, lindane, Chinese mugwort reagent, Di's reagent, DDT, dioxin, Polychlorinated biphenyls, hexachloro-benzene are particularly noticeable.Because this class material has extended residual, biological accumulation, half volatile and high toxicity, is classified as persistence organic pollutant by Convention of Stockholm.Significant to its disinfection.
Bactericide and timber preservative that hexachloro-benzene can be used as seed use, and can also be used to produce pentachlorophenol, fluorocarbon.When producing some chlorohydrocarbons, can produce the hexachloro-benzene accessory substance, also contain hexachloro-benzene in some agricultural chemicals.The approach that hexachloro-benzene enters environment comprises waste water, air and the flue gas of incineration of waste generation and the release of flying dust that contains these products.The use of agricultural chemicals makes hexachloro-benzene form pollution of area source.The chemical property of hexachloro-benzene is stable, is difficult to biodegradation, exists lastingly in environment.To mainly be present in the vapor phase after being discharged in the atmosphere, it is extremely slow to degrade.The whole world migration of long distance may take place.Wet deposition and the dry deposition hexachloro-benzene in can the physical removal atmosphere.To obviously be assigned in bed mud and the suspension after entering water body.In water, very strong suction-operated is arranged with bed mud.The mankind can be exposed to hexachloro-benzene by ambient air, contaminated drinking water and food, contaminated soil and occupational environment.In view of hexachloro-benzene is a material representative in the organochlorine compound, the method for its dechlorination also is applicable to other organochlorine compound.
Now, the academia of countries in the world, industrial quarters, government department all to numerous organochlorine compounds particularly many chlorine organic compound carry out risk assessment, and studied multiple treatment technology and be used to administer of the pollution of these industrial products environment.Existing studies show that, dechlorination are to eliminate the effective ways that this class material pollutes, as electrochemistry dechlorinating process [Wirtz, M.; Klucik, J.; Rivera, M.J.Am.Chem.Soc.2000,122,1047.], photochemistry dechlorinating process [Betterton, E.A.; Hollan, N.; Zhijie, L.Environ.Sci.Technol.2000,34,1229.], ultrasonic dechlorinating process [Teo, K.C.; Xu, Y.; Yang, C.Ultrason.Sonochem.2001,8,241], micro-reduction dechlorinating process [Wiegel, J.; Wu, Q.FEMS Microbiol.Ecol.2000,32,1.], radiation and thermal reduction dechlorinating process [Yamamoto, Y; Tagawa, S.Environ.Sci.Technol.2001,35,2122.].And study at most is chemical method, promptly by reduction reaction, makes the organochlorine compound dechlorination, reduces or eliminates its toxic action.
The most important chemical reaction that organochlorine compound is carried out the hydrogenation dechlorination is catalytic hydrogenation [Rylander, P.Hydrogenation Methods; Academic Press:New York, 1985, Chapter 12.], reducing agent is metal or metallic compound [Lunin, V.V. at a low price; Lokteva, E.S.Russ.Chem.Bull.1996,45,1519.], metal hydride or compound metal hydride [Yoon, N.M.Pure Appl.Chem.1996,68,843.], have the neutrality of strong nucleophilicity or reagents for anion [p 806. for Imamoto, I.In ref 21a], [Fry, A.J.In ref 21a, pp 988-990.].In numerous method of reducing, the hydrogenation dechlorination reaction that metal participates in has obtained using widely, and antichlor is metal simple-substance, metallo-organic compound and some inorganic metal compound.
In numerous inorganic metal compounds, calcium oxide (CaO) is widely used as the antichlor of organochlorine compound because of it cheaply is easy to get.Hall, A.K.[Hall, A.K.; Harrowfield, J.M.; Hart, R.J.; McCormic, P.G.Environ.Sci.Technol.1996,30,3401.] etc. adopt the method for mechanochemistry, CaO and DDT are put into the steel cylinder that is full of argon gas seal, the mode by the ball mill ball milling makes the DDT dechlorination, has obtained good effect at low temperatures.Zhang, Q.[Zhang, Q.; Saito, F.; Ikoma, T.; Et al.Environ.Sci.Technol.2001,35,4933-4935.] etc. when CaO and PCB carry out ball-milling reaction, add quartzyly, improved dechlorination efficiency.
United States Patent (USP) 5,648 has been described a kind of method of handling noxious materials such as DDT, PCBs with CaO No. 591.As, DDT and CaO, stainless steel ball are placed the long-time fully grinding of warp in the steel vessel, realize dechlorination to DDT.Product detects through GC-MS, gas-chromatography electron capture detector, X-ray diffraction, proves that organochlorine is converted into inorganic chlorine fully, and reactive organometal compound in the cracking gas, residual solid composition are C, CaCl 2, Ca (OH) 2And remaining CaO.
United States Patent (USP) 5,242 has been described a kind of method of handling the bed mud that is polluted by PCB with CaO for No. 601.CaO is put into agitating device with bed mud fully mix, stir, exothermic reaction takes place, discharge the gas that produces, obtain flammable, crisp, the scentless product of property, this product is changed in the incinerator burn, the Ca (OH) that generates 2Be decomposed into callable CaO, other inorganic matter, organic matter are converted into the ash content of inertia.Grind the CaO and the ash content of gained.In the gas infall process, isolate the heavy ends in the ash content, carry out landfill disposal, the CaO of gained and residue ash content reusable edible.
United States Patent (USP) 6,490 has been described a kind of method that PCBs oil is converted into available material No. 887.This method comprised for three steps: chemical breakdown, granulating, thermal decomposition process.Chemical decomposition process adopts the CaO that coats with vegetable oil, quartz porphyry powder as distintegrant.Far infrared that discharges from quartz porphyry and CaO acting in conjunction make it to decompose in PCBs oil, obtain the powder of saliferous; Granulating is about to the powder sclerosis, makes particle afterwards; Thermal decomposition process is under the condition that is higher than the PCBs pyrolysis temperature, makes the particle fusing, becomes slag, can be used for building or Agricultural Materials after the cooling.
Summary of the invention
The object of the present invention is to provide a kind of new method of organochlorine compound being carried out dechlorination, this method has that cost is low, equipment is simple, the reaction time is short, is easy to realize, low power consumption and other advantages, has important practical value, can under lower temperature, realize dechlorination by single treatment to organochlorine compound.
For achieving the above object, the present invention is with calcium oxide (CaO) and iron oxide (Fe 2O 3) mixture as antichlor, this antichlor and organochlorine compound are placed in the container, antichlor with the abundant mixing of organochlorine compound, contact, to improve reaction rate and dechlorination efficiency, can realize the dechlorination of organochlorine compound.Along with the rising of system temperature, the prolongation in reaction time can reduce CaO and Fe 2O 3Consumption.In fact, the mass ratio of rising temperature, raising antichlor and organochlorine compound can be realized the dechlorination of organochlorine compound in the short period of time.The preferable reaction condition of the present invention is: the quality of antichlor is more than 10 times or 10 times of organochlorine compound quality, and reaction temperature is 200-500 ℃, is preferably 200-300 ℃, and the reaction time is 0.5-2 hour, is preferably 0.5-1 hour.
In the used antichlor, Fe 2O 3The mass ratio that accounts for antichlor is 1%-50%.This antichlor is with CaO and Fe 2O 3Do preliminary treatment such as drying, dehydration, make its particle diameter, mix then less than 500 microns.
In the antichlor of the present invention, with Fe 3O 4Substitute Fe 2O 3, MgO substitutes CaO, can make the organochlorine compound dechlorination equally.
Antichlor of the present invention can also be compound calcium ferriferous oxide.
With the research report discussed in the background technology and the United States Patent (USP) enumerated with after the technology of the present invention content is compared, the present invention and background technology part inequality as can be seen:
1, adopts CaO and Fe 2O 3Mixture or the calcium iron compound oxide to the dechlorination of aromatic series chloro organic cpd.
2, the dechlorination reaction temperature is lower, can realize complete dechlorination at 300 ℃.
Description of drawings
For further understanding being arranged to the present invention, also be described in detail in conjunction with the accompanying drawings with embodiment below, wherein:
Fig. 1 has shown the relation in dechlorination efficiency of the present invention and reaction time.
Fig. 2 has shown the relation of dechlorination efficiency of the present invention and reaction temperature.
Fig. 3 is a reaction process schematic diagram of the present invention.
The specific embodiment
At first see also Fig. 3, be reaction process schematic diagram of the present invention.Basic fundamental route of the present invention be with chlorine-containing organic waste and 10 times or 10 times more than the quality calcium oxide and the mixture (or calcium iron compound oxide) of iron oxide, add in the blender fully mixing, wherein Fe 2O 3The mass ratio that accounts for antichlor is 1%-50%.The introducing of material behind the mixing is had in the reactor of agitating device, under 200-500 ℃, reacted 0.5-2 hour, finish dechlorination reaction chlorine-containing organic waste.
Need to prove 1) reactor of the present invention can utilize known equipment to carry out.2) Fe 3O 4Substitute Fe 2O 3, MgO substitutes CaO, is that those skilled in the art can understand.
Embodiment 1
With calcium oxide, iron oxide grind, sieve, drying.The hexachloro-benzene of 2mg, the calcium oxide of 100mg and the iron oxide mixture of 100mg are placed 1.38cm 3Closed container in fully mix, in the time of 300 ℃ the reaction 1 hour.Reacted residue is stripped to organic facies with pure water by n-hexane extraction, the impurity that flush away is water-soluble, and the organic product of gained hexane solution behind GC/MS check and analysis dechlorination reaction shows that hexachloro-benzene is by complete dechlorination.After the remaining solid matter drying,, show that residue is CaO, Fe through the X-ray diffraction analysis inorganic compound 2O 3, CaCl 2, CaCO 3Deng.
Embodiment 2
With calcium oxide, iron oxide grind, sieve, drying.The hexachloro-benzene of 2mg, the calcium oxide of 100mg and the iron oxide mixture of 100mg are placed 1.38cm 3Closed container in fully mix, in the time of 300 ℃ the reaction, the reaction time was respectively 5 minutes, 10 minutes, 30 minutes, 60 minutes.Reacted residue is stripped to organic facies with pure water by n-hexane extraction, the impurity that flush away is water-soluble, the organic product of gained hexane solution behind GC/MS check and analysis dechlorination reaction.Dechlorination efficiency when by analysis, calculating 5 minutes, 10 minutes, 30 minutes, 60 minutes is respectively 66.6%, 78.1%, 95.7%, 99.8%.The relation in dechlorination efficiency and reaction time as shown in Figure 1.
Embodiment 3
With calcium oxide, iron oxide grind, sieve, drying.The hexachloro-benzene of 2mg, the calcium oxide of 100mg and the iron oxide mixture of 100mg are placed 1.38cm 3Closed container in fully mix, reaction is one hour during respectively at 200 ℃, 300 ℃, reacted residue is by n-hexane extraction, with pure water organic facies is stripped, the impurity that flush away is water-soluble, the organic product of gained hexane solution behind GC/MS check and analysis dechlorination reaction, by analysis, the dechlorination efficiency when calculating 200 ℃, 300 ℃ is respectively 49.1%, 99.8%.The relation of dechlorination efficiency and reaction temperature as shown in Figure 2.
Embodiment 4
With calcium oxide, iron oxide grind, sieve, drying.The calcium oxide of the hexachloro-benzene of 2mg, 100mg is placed 1.38cm with the iron oxide mixture of 100mg, 80mg, 60mg, 40mg, 20mg respectively 3Closed container in fully mix, in the time of 300 ℃ the reaction one hour.Reacted residue is stripped to organic facies with pure water by n-hexane extraction, the impurity that flush away is water-soluble, the organic product of gained hexane solution behind GC/MS check and analysis dechlorination reaction.By analysis, calculate the dechlorination efficiency of iron oxide when being 100mg, 80mg, 60mg, 40mg, 20mg and be respectively 99.8%, 83.9%, 78.5%, 68.5%, 58.6%.The consumption of iron oxide and the relation of dechlorination efficiency are as shown in table 1.
Table 1
CaO(mg) Fe 2O 3(mg) HCB(mg) Dechlorination efficiency (%)
100 100 100 80 2 2 99.8 83.9
100 100 100 60 40 20 2 2 2 78.5 68.5 58.6
Embodiment 5
With calcium oxide, iron oxide grind, sieve, drying.The hexachloro-benzene of 2mg is placed 1.38cm with the antichlor of 200mg, 80mg, 40mg, 20mg respectively 3Closed container in fully mix, in the time of 300 ℃ the reaction one hour, the mass ratio of calcium oxide and iron oxide is 1: 1 in the antichlor.Reacted residue is stripped to organic facies with pure water by n-hexane extraction, the impurity that flush away is water-soluble, the organic product of gained hexane solution behind GC/MS check and analysis dechlorination reaction.By analysis, calculate the dechlorination efficiency of antichlor when being 200mg, 80mg, 40mg, 20mg and be respectively 99.8%, 78.1%, 77.7%, 54.8%.The consumption of antichlor and the relation of dechlorination efficiency are as shown in table 2.
Table 2
CaO(mg) Fe 2O 3(mg) HCB(mg) Dechlorination efficiency (%)
100 40 20 10 100 40 20 10 2 2 2 2 99.8 78.1 77.7 54.8
Embodiment 6
The hexachloro-benzene of 2mg is placed 1.38cm 3Closed container in, in the time of 300 ℃ the reaction 4 hours, dechlorination reaction does not take place; The hexachloro-benzene of 2mg and the CaO of 200mg are placed 1.38cm 3Closed container in, in the time of 300 ℃ the reaction 4 hours, dechlorination efficiency 49.6%; With the hexachloro-benzene of 2mg and the Fe of 200mg 2O 3Place 1.38cm 3Closed container in, in the time of 300 ℃ the reaction 1 hour, dechlorination efficiency is 38.2%; The hexachloro-benzene of 2mg, the calcium oxide of 100mg and the iron oxide mixture of 100mg are placed 1.38cm 3Closed container in fully mix, in the time of 300 ℃ the reaction 1 hour, dechlorination efficiency is 99.8%.Dechlorination effect in the time of 300 ℃ under four kinds of different conditions is as shown in table 3.
Table 3
CaO(mg) Fe 2O 3(mg) HCB(mg) Reaction time (h) Dechlorination efficiency (%)
0 200 0 100 0 0 200 100 2 2 2 2 4 4 1 1 49.6 38.2 99.8
Above invention has been described in conjunction with the specific embodiment, but it will be understood by those skilled in the art that the described specific embodiment just is used for helping to understand purpose of the present invention, implementation method and effect, is not to be used for limiting the present invention.Not leaving under the claims of the present invention scope and spirit situation of the present invention, can make various changes and modification to the present invention.

Claims (4)

1, a kind of method to the organochlorine compound dechlorination is an antichlor with the mixture of calcium oxide and iron oxide, antichlor and hexachloro-benzene is placed in the container mix, and in 200-500 ℃ of reaction 0.5-2 hour, realizes the dechlorination to hexachloro-benzene;
To account for the mass ratio of antichlor be 1/6-1/2 to iron oxide in the described antichlor;
Described antichlor addition is more than 10 times or 10 times of organochlorine compound quality.
2, the method for claim 1 is characterized in that, reaction temperature is 200-300 ℃.
3, the method for claim 1 is characterized in that, the reaction time is 0.5-1 hour.
4, the method for claim 1 is characterized in that, the particle diameter of antichlor is less than 500 microns.
CNB2003101029418A 2003-10-31 2003-10-31 Method for dechloridizing organochloric compound Expired - Fee Related CN1302834C (en)

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CN100354030C (en) * 2004-11-01 2007-12-12 中国科学院生态环境研究中心 Dechlorination agent and preparation method thereof
CN100441519C (en) * 2005-05-26 2008-12-10 北京化工大学 Method for eliminating chlorine-containing organic matter in water and dechlorine material
CN102127464B (en) * 2009-10-22 2013-09-04 中国石油化工股份有限公司 Method for removing organochlorine from hydrocarbon oil
CN102311162A (en) * 2010-06-30 2012-01-11 中国科学院生态环境研究中心 Treatment method for thermocatalysis degradation of polychlorinated biphenyl pollutant by using magnesium oxide
CN104722304B (en) * 2012-01-16 2017-10-24 南开大学 The mesoporous calcium analysis ferriferous oxide composite catalyst of many chlorine aromatic hydrocarbons of catalysis oxidation
CN102836722B (en) * 2012-09-06 2014-10-15 西安近代化学研究所 Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst
CN103861598A (en) * 2012-12-17 2014-06-18 南开大学 Preparation of calcium-doped iron oxide hollow sphere and application of hollow sphere to catalytically oxidize chloro-substituted volatile organic compounds
CN105749855B (en) * 2014-12-19 2018-12-25 中国石油天然气股份有限公司 Liquid phase antichlor and its preparation method and application
CN107670219B (en) * 2017-09-27 2020-05-15 鲁东大学 Method for treating DDT compounds in stock by combining mechanical grinding and catalytic reduction
CN110000186A (en) * 2019-02-28 2019-07-12 翁源广业清怡食品科技有限公司 The recycling processing method of waste in a kind of sucrose trichloride production process
CN114160566B (en) * 2021-12-24 2023-04-07 武汉理工大学 Mechanochemical method for decomposing hexachlorobenzene by using natural mineral additive

Citations (3)

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US5242601A (en) * 1991-06-06 1993-09-07 Alternative Technologies For Waste, Inc. Sludge treatment with CaO or CaC2 and recovery of CaO therefrom
CN1147977A (en) * 1996-04-26 1997-04-23 湖北省化学研究所 Refined antichlor and method for preparing same
US5648591A (en) * 1992-12-18 1997-07-15 University Of Western Australia Toxic material disposal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242601A (en) * 1991-06-06 1993-09-07 Alternative Technologies For Waste, Inc. Sludge treatment with CaO or CaC2 and recovery of CaO therefrom
US5648591A (en) * 1992-12-18 1997-07-15 University Of Western Australia Toxic material disposal
CN1147977A (en) * 1996-04-26 1997-04-23 湖北省化学研究所 Refined antichlor and method for preparing same

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