CN104147745B - Method for removing volatile halocarbons in environment through chemical conversion - Google Patents
Method for removing volatile halocarbons in environment through chemical conversion Download PDFInfo
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- CN104147745B CN104147745B CN201410418319.6A CN201410418319A CN104147745B CN 104147745 B CN104147745 B CN 104147745B CN 201410418319 A CN201410418319 A CN 201410418319A CN 104147745 B CN104147745 B CN 104147745B
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Abstract
The invention relates to a method for removing volatile halocarbons in environment through chemical conversion, and belongs to the technical field of environmental engineering. Gas or liquid containing the volatile halocarbons reacts with a dehalogenation agent under the heating condition, and the volatile halocarbons in the environment are removed. The method is specially characterized in that the gas or the liquid containing the volatile halocarbons is led into a dehalogenation agent bed layer after drying pretreatment, the halocarbons and the dehalogenation agent react at the temperature of 150 DEG C to 700 DEG C to generate CO2, H2O, gaseous metal halides and the like, generated gaseous substances are blown through carrier gas to flow out of the bed layer, the gaseous substances pass through an absorption cell to be absorbed and treated, exhausted tail gas does not contain toxic substances, and the halocarbons do not exist in residue in the bed layer. At the low reaction temperature, the method can completely remove the halocarbons used for reaction. Compared with traditional methods of physical absorption, high-temperature burning, metal reduction and the like, the method has the advantages of being short in repairing period, thorough in conversion, free of generating secondary pollution and the like.
Description
Technical field
The present invention relates to a kind of minimizing technology of Volatile Organohalides, especially relate to a kind of chemical conversion and remove in environment
The method of Volatile Organohalides, belongs to field of environment engineering.
Background technology
Volatile Organohalides have that density is big, low boiling point, viscosity are little, be insoluble in the characteristics such as water, be widely used in chemical industry,
The fields such as medicine, process hides, electronics, dry-cleaning, if its mismanagement in use, preservation, processing procedure is easily advanced into environment
In.These materials exposing in the environment have great hazardness to human body and environment, and many of compound is due to having
Volatility and easily by skin and mucosa absorption, or transmitted by food chain and be finally enriched in human body, human body is caused serious harm.
Determination of Multiform Volatile Halogenated Hydrocarbons is considered to have " three cause effect " (carcinogenic, teratogenesis, mutagenesis) and suspicious " three cause effect ", therefore,
Volatile Organohalides are always the pollutant of countries in the world priority acccess control.
Volatile Organohalides stable chemical nature, difficult degradation in the environment, existing processing method is divided into Physical, and (heat is de-
Attached method, steam extraction process, absorption method, extraction etc.), chemical oxidization method (burning method, peroxide oxidation method, Ozonation,
Fenton oxidation method), chemical reduction method (zeroth order iron-deoxidize, bimetallic reducing process), bioanalysises (aerobic method, anaerobic process).
Patent CN101530858A (2009) discloses a kind of VOCs-contaminated Soils thermal desorption repair process system
System, including feed system, heat source system and control system, also includes thermal desorption system and exhaust gas processing device, wherein thermal desorption
System is made up of air-introduced machine and Re Ti converter, and exhaust gas processing device is made up of cleaner unit and alkali liquor absorption tower.This invention is being processed
During the contaminated soil of major pollutants volatility/semi-volatile organic matter, although equipment cost compared with external like product
Be about its 1/3～1/5, but the clean-up effect of contaminated soil processing major pollutants volatility/semi-volatile organic matter only may be used
To reach 70%～80%.
Heron etc. (Environmental Science and Technology, 1998,32：1474-1481) with trichlorine
Ethylene pollutant are object of study, have carried out resistance heating Investigation on intensification in two dimension soil case, test result indicate that, at 23 DEG C
Under, the removal efficiency of trichloro ethylene very low it is contemplated that the removal time will exceed 1 year；At 85 DEG C and 100 DEG C, the moving of trichloro ethylene
Mobile Communication's amount increased 2.6 times and 19 times respectively；Through the heat treated of 37 day time at 100 DEG C, the removal effect of trichloro ethylene
Rate reaches 99.8%.
Patent CN101524703A (2009) discloses a kind of ex-situ repair system of petroleum hydrocarbon contaminated soil and operation side
Method, is provided with extraction tower in the renovation technique of petroleum hydrocarbon contaminated soil, and realizes operating continuously.Described extraction tower includes
Hopper, feeder, solids distribution device, liquid distribution trough and discharger；Extraction tower sidewall bottom and top are respectively equipped with solvent and enter
Mouth and solvent outlet；Top of tower and bottom set solids distribution device and liquid distribution trough respectively；Top and bottom tap into glassware respectively
And discharger.This device is desorbed efficiency high, and, up to more than 90%, the soil types being suitable for repairing is wide for extraction partial removal rate, but
It is to there is a problem of that pollutant need to separate and post processing with extractant.
Li Shupeng etc. (environmental project, in August, 2013 the 4th phase of volume 31) adopts Zero-valent Iron-slow release carbon technique to by chloro
The underground reservoir of hydrocarbon pollution carries out pilot scale repairing research.During pilot scale, water-bearing layer from chlorohydrocarbon to underground 9～18m that polluted by
(volume 900m3) injection 7200kg Zero-valent Iron-slow release carbon medicament.Periodic monitoring is carried out to underground water pollutant, result shows：
Zero-valent Iron-slow release carbon technique can be efficiently by the chlorinated hydrocarbon contaminants dealuminated USY cataluyst in underground reservoir.Wherein 1,2- dichloro
The clearance of ethane reaches more than 99.9%, and the clearance of 1,1- dichloroethanes reaches more than 86%, the clearance of chloroform reach 98% with
On.But Zero-valent Iron has unstable, transport transfer in atmosphere the drawback such as will carry out when using under given conditions.
He little Juan etc. (water purification technology, 2007,26 (3)：11-15) study Ni/Fe bimetallic pair under batch experimental condition
CCl4(CT)、CHCl3And CH (TCM)2Cl2(DCM) reductive dechlorination results of property shows, Ni/Fe bimetallic can be effectively to CT
Carry out dechlorination with TCM, but there is no dechlorination effect to DCM；Under similar reaction condition, Ni/Fe bimetallic takes off to CT and TCM
Chlorine effect is better than Zero-valent Iron.
Muftikina R etc. (Water Research, 1995,29：2434-2439) add your gold in first report Fe
The method that metal catalyst bimetallic processes halogenated hydrocarbons, the dechlorination efficiency that dichloroethylene, trichloro ethylene, tetrachloroethylene are processed
Very high.Quan Xie etc. (Journal of Dalian University of Technology Total, 1997,37 (1)：25-20) have studied the Pd/Fe that palladium rate is 0.05% to three
The dechlorination efficiency of vinyl chloride, the dechlorination rate in 5 minutes reaches 96%.
Bellamy et al. (Research Journal WPCF, 1991,63 (2)：120-128.) carry out O3/H2O2Body
System processes dichloroethylene, trichloro ethylene, tetrachloroethylene, the experiment of carbon tetrachloride, and result shows O3/H2O2Degraded to chloro footpath
Efficiency is very high, and oxidation rate is with O3Delivery rate increase and become big.But O3/H2O2The continuous action time of system is short, is difficult to
Control its reaction rate.
Speny etc. (Journal of Environmental Engineering.2006,132 (2)：199-213) will
Na2S2O8Be injected into rich in the chiltern water-bearing layer of natural iron mineral it can be observed that trichloro ethylene, tetrachloroethylene and four chlorinations
The fast degradation phenomenon (clearance reaches 83%) of carbon, this natural iron mineral showing in water-bearing layer can be equally used for being catalyzed over cure
The chemical oxidation to trichloro ethylene etc. for the hydrochlorate.
Wu Jiayi etc. (Chinese environmental science and technology, 2011,31 (5)：810-814.) carry out KMnO4In oxidation removal sandy loam
The experimental study of trichloro ethylene, determines KMnO using orthogonal experiment4The optimum condition of oxidation trichloro ethylene, and carried out earth pillar
In-situ oxidation is tested, and result shows to adopt KMnO4After solution drip washing earth pillar 12d, trichloro ethylene oxygenation efficiency all reaches more than 88%,
And reduction rate of flow in rinse can improve oxygenation efficiency.Chlorohydrocarbon is through KMnO4After oxidation, can dechlorination completely, and the poison of catabolite
Property be less than original matter KMnO4Nontoxic to microorganism, can be combined with biological restoration.But utilize KMnO4Oxidation processes are subject to chlorohydrocarbon
During the subsoil water of pollution, in KMnO4Water-fast MnO will be produced in oxidizing process2By-product, the hole to underground environment
The phenomenon that results in blockage is so that subsurface flow cannot current-carrying KMnO4Solution, leads to KMnO4Can not effectively contact with pollutant, from
And so that oxidation reaction is slowed down.
Content of the invention
The purpose of the present invention is exactly to provide to overcome the defect that above-mentioned prior art exists that a kind of repairing efficiency is short, turn
Change the method that chemical conversion that is thorough, not producing secondary pollution removes Volatile Organohalides in environment.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method that chemical conversion removes Volatile Organohalides in environment, by the gas containing Volatile Organohalides or liquid
Body is reacted in a heated condition with agent, removes the Volatile Organohalides in environment.
Described Volatile Organohalides be chloromethanes, dichloromethane, chloroform, bromofom, carbon tetrachloride, 1,1- dichloroethanes,
1,2- dichloroethanes, 1，1，1-trichloroethane, vinyl trichloride, sym.-tetrachloroethane, unsym.-tetraehloroethane,
Vinyl chloride, vinylidene chloride, cis -1,2-dichloroethene, anti-form-1,2- dichloroethylene, sym-dibromoethane, trichloro ethylene, four
Any one in vinyl chloride, 1,2- dichloropropane, glyceryl trichloride, two bromochloromethanes or a bromodichloromethane, or
It is the mixture of their arbitrary proportions.
Gas containing Volatile Organohalides, is Volatile Organohalides itself or by gaseous state halogenated hydrocarbons, N2、O2, Ar, He or
The mixed gas of their arbitrary proportion mixed gas dilutions；
Liquid containing Volatile Organohalides, is Volatile Organohalides itself or by liquid halogenated hydrocarbons and other organic liquor
Body such as alkane, aromatic hydrocarbon are with the liquefied mixture of arbitrary proportion mixed diluting.
In gas containing Volatile Organohalides or liquid, the concentration of halogenated hydrocarbons is in the concentration range of 1ppm～100%.
Described agent is the mixture of metal-oxide or zeolite molecular sieve or the two arbitrary proportion.
Described metal-oxide is A2O3Or BO2, wherein A is positive trivalent metal, and B is positive 4 valency metals.
Described A2O3, including A that naturally occur or synthetic2O3；Can be unformed, such as surge aluminum stone, plan are thin
Diaspore etc.；Can also be for having certain crystal formation, such as χ-A2O3、η-A2O3、γ-A2O3、δ-A2O3、κ-A2O3、θ-A2O3、ρ-
A2O3Or α-A2O3, preferably agent is γ-A2O3.
Described BO2Including BO that naturally occur or synthetic2；Can be unformed or have certain
Crystal formation, preferably agent is Tetragonal BO2.
Described zeolite molecular sieve is selected from micro-pore zeolite molecular sieve, mesopore zeolite molecular sieve or two-dimensional molecular sieve or three appoints
The mixture of meaning ratio.
Described micro-pore zeolite molecular sieve be selected from A type (3A, 4A, 5A), X-type (10X, 13X), Y type, MFI type, MOR type,
Beta (β) type, FER type, SAPO-34 molecular sieve.Dehalogenation effect is preferably X-type or Y type molecular sieve.
Described mesopore zeolite molecular sieve is selected from MCM-41 molecular sieve or MCM-48 molecular sieve.
Described two-dimensional molecular sieves as acid montmorillonite, Acidic Bentonite, Emathlite or pillared montmorillonite；
Wherein pillared montmorillonite is that acid montmorillonite, Acidic Bentonite and Emathlite inorganic material are modified gained.
Described agent and porous mass coexist, when being reacted, the gross mass of agent institute in processing sample
The mass percent accounting for is more than 10%；
Described porous mass is SiO2, activated carbon or clay.
Gas containing Volatile Organohalides or liquid are reacted at 150～700 DEG C with agent, preferably react
Temperature range is 200～600 DEG C.
The present invention is in order to realize quick, the thorough conversion removing of described Volatile Organohalides, the technical scheme being adopted
It is：By the gas containing the Volatile Organohalides or liquid bed by agent, reacting by heating, generate CO2、H2O and distillation
The gaseous materials such as metal halide, tail gas directly discharges after water or alkali liquor absorption, and in bed, residue does not contain the residual of halogenated hydrocarbons
Stay, nontoxic, also can directly reclaim or landfill disposal.
This process occur chemical reaction as follows (with CCl4With BO2As a example reaction)：
BO2+CCl4→BCl4↑+CO2↑
BCl4+NaOH→B(OH)4+ NaCl, B are positive 4 valency metals
Remove Volatile Organohalides with the inventive method, its process can be divided into 3 steps：
(1) agent preprocessing process is dried：Agent is placed in dry gas (as N2, air or theirs is mixed
Close gas) or vacuum in, at 100～250 DEG C heat, remove agent in free moisture.
(2) course of reaction of halogenated hydrocarbons and agent：At 150～750 DEG C, be passed through in described agent bed containing
The gas of Volatile Organohalides or liquid, halogenated hydrocarbons are reacted with agent, generate CO2、H2O and the metal halide of distillation
Deng gaseous material.
(3) tail gas absorption and agent reaction after residue processing procedure：With water or alkali liquor absorption tail gas, the master of this process
Syllabus be absorb gas in metal halide so as to be converted into metal hydroxidess；Have in agent after reaction
It is not involved in the material reacting (as SiO2) remain, these residues are nontoxic, and the method toppled over using landfill or directly is carried out
Process.
This process does not produce secondary pollution, quick to the removing of halogenated hydrocarbons, thoroughly, and device is few, operation simple it is easy to real
Apply.
Compared with prior art, the present invention is applied to the reaction elimination of common Volatile Organohalides, Volatile Organohalides
Can be gaseous can also be liquid, can be single substance can also be mixture.Agent used by the present invention
(A2O3、BO2Deng metal-oxide, and zeolite molecular sieve etc.) physics and chemical characteristic can manual control, can be according to processing need
Above-mentioned agent is carried out with modification, agent wide material sources, consumption and reaction temperature can be according to halogenated hydrocarbons itself
Reactivity, concentration and flow determine.Dehalogenation reaction process is simple, and desired reaction temperature is moderate, under relatively low reaction temperature,
Multiclass chlorohydrocarbon can be removed completely.The tail gas that the dehalogenation reaction generates carries out after absorption process through absorption cell, in the tail gas of discharge
Without no halogenated hydrocarbons in the residue in noxious substance, and bed.The method, compared with traditional treatment method, has repairing efficiency
Short, conversion thoroughly, the advantages of do not produce secondary pollution.The method can be applicable to place and the underground polluted by volatile organic matter
The improvement of water and reparation.
Brief description
Fig. 1 is for ReY type molecular sieve and USY type molecular sieve to CCl4Conversion ratio change over curve.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Under different temperatures, metal-oxide is to CCl4Removal effect
By metal-oxide (Al2O3、SnO2、TiO2Deng) activate 4h in Muffle furnace at 500 DEG C, take 0.8g to put into solid
In fixed bed reactor, it is passed through the CCl of 1010ppm4/N2Gas, gas flow rate 37.7ml/min, heats at 200 DEG C～400 DEG C
Reaction, CCl under different temperatures4Conversion ratio as shown in table 1.
Under table 1 different temperatures, metal-oxide is to CCl4Removal effect
Embodiment 2
Metal composite oxide is to CCl4Removal effect
By composition metal metal-oxide Al2O3·SnO2And Al2O3·2SnO2Activate 4h in Muffle furnace at 500 DEG C,
Take 0.8g to put in fixed bed reactors, be passed through the CCl of 1010ppm4/N2Gas, gas flow rate 37.7ml/min, in 150 DEG C～
Reacting by heating at 350 DEG C, CCl under different temperatures4Conversion ratio as shown in table 2.
Table 2 metal composite oxide is to CCl4Removal effect
Embodiment 3
A type molecular sieve is to CCl4Removal effect
A type molecular sieve (3A type, 4A type, 5A type) is activated 4h in Muffle furnace at 500 DEG C, takes 0.8g to put into fixed bed
In reactor, it is passed through the CCl of 1010ppm4/N2Gas, gas flow rate 37.7ml/min, reacting by heating at 150 DEG C～300 DEG C,
CCl under different temperatures4Conversion ratio as shown in table 3.
Table 3 A type molecular sieve is to CCl4Removal effect
Embodiment 4
X-type molecular sieve is to CCl4Removal effect
X-type molecular sieve (10X type, 13X type etc.) is activated 4h in Muffle furnace at 500 DEG C, takes 0.2g to put into fixed bed
In reactor, it is passed through the CCl of 1010ppm4/N2Gas, gas flow rate 37.7ml/min, reacting by heating at 150 DEG C～300 DEG C,
CCl under different temperatures4Conversion ratio as shown in table 4.
Table 4 X-type molecular sieve is to CCl4Removal effect
Embodiment 5
Y type molecular sieve is to CCl4Removal effect
Y type molecular sieve (NaY type, HY type, USY type, ReY type etc.) is activated 4h in Muffle furnace at 400 DEG C, takes 0.2g
Put in fixed bed reactors, be passed through the CCl of 1010ppm4/N2Gas, gas flow rate 37.7ml/min, in 150 DEG C～300 DEG C
Lower reacting by heating, CCl under different temperatures4Conversion ratio as shown in table 5.
Table 5 Y type molecular sieve is to CCl4Removal effect
Embodiment 6
NaY type molecular sieve and bentonite mixtures are to CCl4Removal effect
NaY type molecular sieve is mixed with certain mass ratio (respectively 1: 1,1: 2,1: 4) respectively with bentonite, in mortar
In pulverize mixing, in Muffle furnace at 400 DEG C activate 4h, take 0.2g to put in fixed bed reactors, be passed through 1010ppm's
CCl4/N2Gas, gas flow rate 37.7ml/min, reacting by heating at 150 DEG C～300 DEG C, CCl under different temperatures4Conversion ratio
As shown in table 6.
Table 6 NaY type molecular sieve and bentonite mixtures are to CCl4Removal effect
Embodiment 7
Type ZSM 5 molecular sieve and beta molecular sieve are to CHCl3/CCl4The removal effect of mixed gas
Type ZSM 5 molecular sieve and beta molecular sieve are activated 4h in Muffle furnace at 500 DEG C, takes 0.2g to put into fixed bed
In reactor, it is passed through CHCl in mixed gas3Concentration is 850ppm, CCl4Concentration is 1010ppm, gas flow rate 40ml/min, in
Reacting by heating at 150 DEG C～300 DEG C, CHCl under different temperatures3And CCl4Conversion ratio respectively as shown in table 7, table 8.
Table 7 type ZSM 5 molecular sieve and beta molecular sieve are to CHCl3/CCl4CHCl in mixed gas3Removal effect
Table 8 type ZSM 5 molecular sieve and beta molecular sieve are to CHCl3/CCl4CCl in mixed gas4Removal effect
Embodiment 8
ReY type molecular sieve and USY type molecular sieve are to C2Cl4Removal effect
Molecular sieve 7 and molecular sieve 8 are activated 4h in Muffle furnace at 500 DEG C, takes 4g to put in fixed bed reactors, use
Plunger displacement pump is passed through the C of liquid2Cl4, flow velocity is 2ml/h, reacting by heating at 200 DEG C～400 DEG C, C under different temperatures2Cl4Turn
Rate is as shown in table 9.
Table 9 ReY type molecular sieve and USY type molecular sieve are to C2Cl4Removal effect
Embodiment 9
Response time is to ReY type molecular sieve and USY type molecular sieve and CCl4The impact of reaction conversion ratio
ReY type molecular sieve and USY type molecular sieve are activated 4h in Muffle furnace at 500 DEG C, takes 0.2g to put into fixed bed
In reactor, it is passed through the CCl of 1010ppm4/N2Gas, gas flow rate 45.0ml/min, reacting by heating at 350 DEG C, CCl4's
Conversion ratio changes over as shown in Figure 1.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel
Within protection domain.
Claims (6)
1. a kind of chemical conversion remove Volatile Organohalides in environment method it is characterised in that
By the gas containing the Volatile Organohalides or liquid bed by agent, reacting by heating, generate CO2、H2O and distillation
Metal halide gaseous material, tail gas directly discharges after water or alkali liquor absorption, and in bed, residue does not contain the residual of halogenated hydrocarbons
Stay, directly reclaim or landfill disposal；
Described agent is the mixture of metal-oxide and both zeolite molecular sieves arbitrary proportion；Described agent with many
Hole material coexists, and when being reacted, the mass percent that the gross mass of agent is shared in processing sample is more than 10%；
Described metal-oxide is A2O3Or BO2, wherein A is positive trivalent metal, and B is positive 4 valency metals；
Described zeolite molecular sieve be selected from micro-pore zeolite molecular sieve, mesopore zeolite molecular sieve or two-dimensional molecular sieve or three arbitrarily than
The mixture of example；
Described porous mass is SiO2, activated carbon or clay.
2. a kind of chemical conversion according to claim 1 remove Volatile Organohalides in environment method it is characterised in that
Described Volatile Organohalides are chloromethanes, dichloromethane, chloroform, bromofom, carbon tetrachloride, 1,1- dichloroethanes, 1,2- dichloro
Ethane, 1,1,1- trichloroethane, 1,1,2- trichloroethane, 1,1,2,2- sym-tetrachloroethane, 1,1,1,2- sym-tetrachloroethane, vinyl chloride,
1,1- dichloroethylene, cis -1,2- dichloroethylene, anti-form-1,2- dichloroethylene, sym-dibromoethane, trichloro ethylene, tetrachloroethylene,
Any one in 1,2- dichloropropane, glyceryl trichloride, two bromochloromethanes or a bromodichloromethane, or they appoint
The mixture of meaning ratio.
3. a kind of chemical conversion according to claim 1 remove Volatile Organohalides in environment method it is characterised in that
Gas containing Volatile Organohalides, is Volatile Organohalides itself or by gaseous state halogenated hydrocarbons and N2、O2, Ar, He be with arbitrary proportion
The mixed gas mixing；
Liquid containing Volatile Organohalides, be Volatile Organohalides itself or by liquid halogenated hydrocarbons and other organic liquids with
The liquefied mixture of arbitrary proportion mixed diluting.
4. the method that a kind of chemical conversion according to claim 1 or 3 removes Volatile Organohalides in environment, its feature exists
In, in the gas containing Volatile Organohalides or liquid, the concentration of halogenated hydrocarbons is in the concentration range of 1ppm～100%.
5. a kind of chemical conversion according to claim 1 remove Volatile Organohalides in environment method it is characterised in that
Described micro-pore zeolite molecular sieve is selected from A type, X-type, Y type, MFI type, MOR type, Beta type, FER type or SAPO-34 molecular sieve；
Described mesopore zeolite molecular sieve is selected from MCM-41 molecular sieve or MCM-48 molecular sieve.
Described two-dimensional molecular sieves as acid montmorillonite, Acidic Bentonite, Emathlite or pillared montmorillonite；
Wherein pillared montmorillonite is that acid montmorillonite, Acidic Bentonite and Emathlite inorganic material are modified gained.
6. a kind of chemical conversion according to claim 1 remove Volatile Organohalides in environment method it is characterised in that
Gas containing Volatile Organohalides or liquid are reacted at 150～700 DEG C with agent.
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| CN109909279B (en) * | 2019-03-14 | 2020-01-03 | 中国地质大学（北京） | Medicament and method for synchronously fixing and reducing trichloroethylene in soil and/or underground water |
| CN110917871B (en) * | 2019-11-05 | 2022-03-25 | 河北科技大学 | Method for absorbing and catalytically oxidizing halogenated hydrocarbon by using metal simple substance and/or metal oxide |
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| CN1098326A (en) * | 1992-12-23 | 1995-02-08 | 罗姆和哈斯公司 | Remove and destroy the method for halogenated organic compounds and hydrocarbon compound with porous carbonaceous materials |
| CN1265043A (en) * | 1997-07-23 | 2000-08-30 | 帕克控股公司 | Method for eliminating halogenated and non halogenated waste |
| CN1382072A (en) * | 1999-09-29 | 2002-11-27 | 三井化学株式会社 | Catalyst for decomposing organic hazardous material and method for decomposing organic halides using the same |
| CN1544110A (en) * | 2003-11-20 | 2004-11-10 | 上海交通大学 | Preparation of self-catalyze degradation pesticide |
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2014
- 2014-08-22 CN CN201410418319.6A patent/CN104147745B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098326A (en) * | 1992-12-23 | 1995-02-08 | 罗姆和哈斯公司 | Remove and destroy the method for halogenated organic compounds and hydrocarbon compound with porous carbonaceous materials |
| CN1265043A (en) * | 1997-07-23 | 2000-08-30 | 帕克控股公司 | Method for eliminating halogenated and non halogenated waste |
| CN1382072A (en) * | 1999-09-29 | 2002-11-27 | 三井化学株式会社 | Catalyst for decomposing organic hazardous material and method for decomposing organic halides using the same |
| CN1544110A (en) * | 2003-11-20 | 2004-11-10 | 上海交通大学 | Preparation of self-catalyze degradation pesticide |
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