CN107670219A - The method of mechanical lapping catalysis reduction Combined Treatment stock's DDT class compounds - Google Patents
The method of mechanical lapping catalysis reduction Combined Treatment stock's DDT class compounds Download PDFInfo
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- 230000009467 reduction Effects 0.000 title claims abstract description 39
- 238000011282 treatment Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- -1 DDT class compounds Chemical class 0.000 title claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 title claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 10
- 239000002250 absorbent Substances 0.000 claims abstract description 8
- 230000002745 absorbent Effects 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 3
- 239000003610 charcoal Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 231100000419 toxicity Toxicity 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000007033 dehydrochlorination reaction Methods 0.000 abstract description 5
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 abstract description 3
- LNKQQZFLNUVWQQ-UHFFFAOYSA-N 1-chloro-2,2-bis(4'-chlorophenyl)ethylene Chemical compound C=1C=C(Cl)C=CC=1C(=CCl)C1=CC=C(Cl)C=C1 LNKQQZFLNUVWQQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 abstract 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000003672 processing method Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000002957 persistent organic pollutant Substances 0.000 description 7
- 238000007210 heterogeneous catalysis Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method that mechanical lapping is catalyzed reduction Combined Treatment stock's DDT class compounds；It is characterized in, using mechanical lapping inducible alkaline material by DDT（Or DDD）It is converted into the DDE being easier to by deoxidization, degradation（1,1 pairs of (rubigan) 2,2 dichloroethylene）Or DDMU（1,1 pairs of (rubigan) 2 vinyl chloride）, its dehydrochlorination product is then converted into the material that toxicity is relatively low, is easily biodegradable by being catalyzed reduction；Mechanical grinding method is handled using alkaline matter and DDT class compounds mixed grinding, and treatment temperature is controlled at 20~50 DEG C；And be catalyzed reduction and use loaded noble metal catalyst, by the use of hydrogen as hydrogen source, reduction dechlorination is carried out to the mechanical lapping processing product in liquid-phase system in the presence of alkaline proton absorbent, reaction pressure is 0.1~1.0 MPa, and reaction temperature is controlled at 20~80 DEG C；Efficiency high, reaction condition are gentle, shorten the reaction time, and operation is easily controllable, cost is low, have production and practical value well.
Description
Technical field：
The present invention relates to the processing method of stock's DDT class compounds, at specifically a kind of mechanical lapping-catalysis reduction joint
The method for managing stock's DDT class compounds.
Background technology：
Organochlorine insecticide DDT（Double rubigan trichloroethanes）Once it was widely used as a kind of efficient insecticide, but by
In its have strong carcinogenic, teratogenesis, mutagenicity " three cause effect ", therefore DDT plans in united nations environment in 2001
Administration（UNEP）Pass through《Convention of Stockholm on persistence organic pollutant》In require that the whole world is sought unity of action preferential control
System and the 12 kinds of persistence organic pollutants eliminated（POPs）One of.To developing countries such as China, pact was provided in 2014
The production and use of total ban DDT.
To developing countries such as China,《POPs pacts》Provide the production and use in total ban DDT in 2014.At me
State, DDT production history span half a century, and its cumulative production is about 400,000 tons, account for 20% or so of global DDT productions.
Although world's most countries have been stopped producing and still existed using DDT class agricultural chemicals, its influence to ecological environment,
It can be detected in air, soil, water body, deposit, animals and plants etc., or even also can in domestic water, human serum, milk
Generally detected.Therefore, for stock DDT the characteristics of, research cycle is short, efficiency high processing method is controlled from source
The organochlorine such as system and abatement DDT not only with important scientific meaning and application prospect, while is fulfiled for pollutant to China
《POPs pacts》Also there is important directive significance.
Currently, DDT processing method mainly has physical restoration, biological restoration, incineration method, advanced oxidation processes, chemistry
Reduction dechlorination method etc.；These processing methods respectively have advantage and disadvantage.Physical restoration is a kind of temporary transient, processing method of delay, and
The purpose that pollutant toxicity is completely eliminated is not reaching to, is also possible to bring secondary pollution in transfer process.Biological restoration drops
It is low to solve efficiency comparison, degraded is not thorough enough, and is vulnerable to the influence of DDT toxicity, and this method is mainly for low concentration DDT's at present
Eliminate, and be still in the laboratory exploratory stage.Although burning and the suitable a variety of conditions of advanced oxidization method, high energy consumption, and not
Burn completely and oxidation easily generates the stronger dioxins materials of toxicity and causes secondary pollution.Electronation dechlorinating process is one
Kind effectively degraded DDT method；Wherein, heterogeneous catalysis reduction dechlorination method is because its catalysis material can be with recycling, therefore
Compared with other reduction dechlorination methods, heterogeneous catalysis reduction dechlorination method is a kind of simpler, safe and effective abatement DDT side
Method, but equally exist the problem of hydrogenation products can cause secondary pollution, and the influence of the contaminated thing stability for the treatment of effeciency compared with
Greatly.It can be seen that using the single side such as high temperature incineration, catalysis oxidation, light degradation, biodegradation, reduction dechlorination and catalytic reductive dechlorination
Method is difficult to realize the POPs such as DDT quick, efficient degradation.
The content of the invention：
The present invention seeks to overcome the shortcomings of above-mentioned prior art, there is provided a kind of mechanical lapping-catalysis reduction Combined Treatment stock
The method of DDT class compounds；The processing method for mainly solving existing DDT brings secondary pollution, degradation efficiency than relatively low, degraded
The problems such as not thorough enough and high energy consumption.
The technical solution adopted by the present invention is：The side of mechanical lapping-catalysis reduction Combined Treatment stock's DDT class compounds
Method, it is characterized in that, comprises the following steps：
A mechanical lappings are handled, and pending stock DDT classes compound sample and alkaline matter are induced into its dechlorination by mechanical lapping
Change hydrogen, generate the product of easily hydrogenation degraded；
B is catalyzed reduction treatment, after mechanical lapping processing, adds alcohol-water mixed solution and loaded noble metal catalyst, is used in combination
Hydrogen carries out catalytic reduction reaction, and then obtain mechanical lapping processing product as hydrogen source in the presence of alkaline proton absorbent
Effectively to degrade；
Wherein, alkaline matter is alkaline earth oxide or hydroxide used by described mechanical lapping processing；Described
Alkaline proton absorbent is alkali metal hydroxide used by being catalyzed reduction treatment；
Reduction reaction is carried out at 0.1~1.0 MPa, 20~80 DEG C in described catalysis reduction treatment；Described catalyst adds
Enter the 1.0-5.0% that amount is sample quality.
Further, described mechanical lapping processing step temperature is 20~50 DEG C, described alkaline matter and DDT classes
The mol ratio of compound is 0.8/1~1.5/1.
Further, described alkaline earth oxide is one kind in MgO, CaO, SrO, and described hydroxide is Mg
(OH)2、Ca(OH)2、Sr(OH)2In one kind.
Further, the active component of the catalyst of described catalysis reduction treatment step is noble metal, and active component accounts for
The 0.5~5.0% of catalyst total amount.
Further, described active component is one kind in Pd, Rh, Ru, Pt, Ni, Fe, Co, Ir；Support active component
Carrier be activated carbon, silica gel or alundum (Al2O3) in one kind.
Further, reduction reaction is carried out at 0.1~0.5 MPa, 30~60 DEG C in described catalysis reduction treatment.
Further, the alcohol of described catalysis reduction treatment is methanol, ethanol, normal propyl alcohol, isopropanol, sec-butyl alcohol, tertiary fourth
One kind in alcohol.
Further, described alkali metal hydroxide is one kind in LiOH, NaOH, KOH, RbOH, CsOH；Alkaline matter
Sub- absorbent and the mol ratio of chlorine atom in mechanical lapping processing product are 1.5/1~1/1.5.
A kind of method of mechanical lapping of the present invention-catalysis reduction Combined Treatment stock's DDT class compounds is with having
Technology is compared with prominent substantive distinguishing features and marked improvement, 1, using mechanical lapping inducible alkaline material by DDT（Or DDD）
It is converted into the DDE being easier to by deoxidization, degradation（Double (the rubigan) -2,2- dichloroethylene of 1,1-）Or DDMU（1,1- is double (right
Chlorphenyl) -2- vinyl chloride）, it is relatively low that toxicity then is converted into by being catalyzed reduction by its dehydrochlorination product, is easily biodegradable
Material；2nd, processing method prepares simple, it is not necessary to other special installations；3rd, combination treatment method condition is more gentle, machine
Catalytic reduction reaction can be directly carried out after tool milled processed, transition metal loaded catalyst is urged used in catalytic reduction reaction
Change activity is higher, and catalyst amount is few, and reaction product toxicity substantially reduces；4th, shorten the reaction time, reduce cost and
, can be with persistence organic pollutants such as simple and quick, efficient process stock DDT with more preferable production and practical value.
Brief description of the drawings：
Fig. 1 is existing high concentration DDT heterogeneous catalysis reduction treatment result；
Fig. 2 is the stock DDT of present invention mechanical lapping-heterogeneous catalysis reduction treatment result.
Embodiment：
Following examples are the further explanations to the present invention, but the invention is not restricted to this.Illustrated embodiment is only used for explaining this
Invention, is not intended to limit the scope of the present invention.
The present invention provides carries out mechanical lapping-catalysis also under relatively temperate condition to stock's DDT pollutants sample
Former processing method, dechlorination is carried out to stock's DDT pollutants sample using mechanical lapping in the presence of a basic first
Hydrogen processing；Then the dissolving of alcohol-water mixed solution is added, and adds loaded noble metal catalyst, and by the use of hydrogen as hydrogen source,
Catalysis reduction treatment is carried out to mechanical lapping processing product in the presence of alkaline proton absorbent, reaction pressure is 0.1~1.0
MPa, reaction temperature are controlled at 20~80 DEG C.
Comparative example 1, stock DDT heterogeneous catalysis reduction treatment（Existing processing method）：
Weigh 0.4 g DDT samples, add the isopropanol-water mixed solutions of 80 mL 70% in catalytic reduction reaction kettle, addition
20mg Pd/C catalyst, 0.062 g NaOH are added, by the use of hydrogen as hydrogen source, it is de- that catalysis reduction is carried out to the DDT in liquid phase
Chlorine, reaction pressure are 0.1 MPa, and reaction temperature is controlled at 40 DEG C, react and lead to hydrogen under mechanical agitator stirring, specific knot
Fruit sees Fig. 1.
Embodiment 1,0.4 g DDT samples are weighed, are added in grinder, then add the mg of CaO 18, grinding temperature is
Normal temperature（30 ℃）, the h of milling time 1.0；Then the alcohol-water mixed solutions of 80 mL 70% are added, to catalytic reduction reaction kettle
It is interior, 10mg Pd/C catalyst is added, by the use of hydrogen as hydrogen source, to the DDT dehydrochlorinations in liquid phase in the presence of inorganic base NaOH
Product carries out catalysis reduction treatment, and reaction pressure is 0.1 MPa, and reaction temperature controls at 40 DEG C, reacts and stirred in mechanical agitator
Lower logical hydrogen is mixed, concrete outcome is shown in Fig. 2.
Embodiment 2,1.0 g DDT samples are weighed, are added in grinder, then add different alkaline matters, grinding temperature
Spend for normal temperature, the h of milling time 1.0；Then the isopropanol-water mixed solutions of 80 mL 70% are added, into catalytic hydrogenation reaction kettle,
10 mg Pd/C catalyst are added, by the use of hydrogen as hydrogen source, the DDT dehydrochlorinations in liquid phase are produced in the presence of inorganic base NaOH
Thing carries out catalysis reduction treatment, and reaction pressure is 0.1 MPa, and reaction temperature is controlled at 50 DEG C, is reacted and is stirred in mechanical agitator
Logical hydrogen, concrete outcome are shown in Table 1 down.Dechlorination efficiency=（Chlorinity after chloride content-reaction）/ chloride content }
Embodiment 3,0.4 g DDT samples are weighed, are added in grinder, then add 18 mg CaO, grinding temperature is normal
Temperature, the h of milling time 1.0；Then the isopropanol-water mixed solutions of 80 mL 70% are added, into catalytic hydrogenation reaction kettle, add 20
Mg different loads type noble metal catalysts, by the use of hydrogen as hydrogen source, the DDT dehydrochlorinations in liquid phase are produced in the presence of an inorganic base
Thing carries out catalysis reduction treatment, and reaction pressure is 0.1 MPa, and reaction temperature is controlled at 40 DEG C, is reacted and is stirred in mechanical agitator
Logical hydrogen, concrete outcome are shown in Table 2 down.
Embodiment 4,0.4 g DDT samples are weighed, are added in grinder, then add the mg of CaO 18, grinding temperature point
Wei not be 20 DEG C, 30 DEG C and 50 DEG C, the h of milling time 1.0；Then 80 mL alcohol-water mixed solution is added, it is anti-to catalysis reduction
Answer in kettle, add 20 mg Pd/C catalyst, by the use of hydrogen as hydrogen source, the DDT in liquid phase is taken off in the presence of inorganic base NaOH
Hydrogen chloride product carries out catalysis reduction treatment, and reaction pressure is 0.1 MPa, 0.5 MPa and 1.0 MPa, reaction temperature
Control controls at 20 DEG C, 30 DEG C, 40 DEG C, 60 DEG C and 80 DEG C respectively, reacts and leads to hydrogen, tool under mechanical agitator stirring
Body the results are shown in Table 3.
According to the operating process of above-described embodiment, after reaction terminates, reaction solution is separated with catalyst filtration, recovery catalysis
Agent, due to reactant, the solubility in water is very low with product, is largely dissolved in organic phase, thus organic by extract and separate
Phase, and organic phase is evaporated under reduced pressure, recovery product and obtain 1,1 '-diphenylethane.
Claims (8)
1. the method for mechanical lapping-catalysis reduction Combined Treatment stock's DDT class compounds, it is characterised in that comprise the following steps：
A mechanical lappings are handled, and pending stock DDT classes compound sample and alkaline matter are induced into its dechlorination by mechanical lapping
Change hydrogen, generate the product of easily hydrogenation degraded；
B is catalyzed reduction treatment, after mechanical lapping processing, adds alcohol-water mixed solution and loaded noble metal catalyst, is used in combination
Hydrogen carries out catalytic reduction reaction, and then obtain mechanical lapping processing product as hydrogen source in the presence of alkaline proton absorbent
Effectively to degrade；
Wherein, alkaline matter is alkaline earth oxide or hydroxide used by described mechanical lapping processing；Described
Alkaline proton absorbent is alkali metal hydroxide used by being catalyzed reduction treatment；
Reduction reaction is carried out at 0.1~1.0 MPa, 20~80 DEG C in described catalysis reduction treatment；Described catalyst adds
Enter the 1.0-5.0% that amount is sample quality.
2. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In described mechanical lapping processing step temperature is 20~50 DEG C, and described alkaline matter and the mol ratio of DDT class compounds are
0.8/1~1.5/1.
3. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In described alkaline earth oxide is one kind in MgO, CaO, SrO, and described hydroxide is Mg (OH)2、Ca(OH)2、
Sr(OH)2In one kind.
4. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In the active component of the catalyst of described catalysis reduction treatment step is noble metal, and active component accounts for the 0.5 of catalyst total amount
~5.0%.
5. the method for mechanical lapping according to claim 4-reduction Combined Treatment stock's DDT class compounds, its feature exist
In described active component is one kind in Pd, Rh, Ru, Pt, Ni, Fe, Co, Ir；The carrier for supporting active component is activity
One kind in charcoal, silica gel or alundum (Al2O3).
6. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In reduction reaction is carried out at 0.1~0.5 MPa, 30~60 DEG C in described catalysis reduction treatment.
7. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In the alcohol of described catalysis reduction treatment is one kind in methanol, ethanol, normal propyl alcohol, isopropanol, sec-butyl alcohol, the tert-butyl alcohol.
8. the method for mechanical lapping according to claim 1-reduction Combined Treatment stock's DDT class compounds, its feature exist
In described alkali metal hydroxide is one kind in LiOH, NaOH, KOH, RbOH, CsOH；Alkaline proton absorbent and machinery
The mol ratio of chlorine atom is 1.5/1~1/1.5 in milled processed product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134201A (en) * | 2018-09-11 | 2019-01-04 | 鲁东大学 | The heterogeneous catalytic hydrogenation defluorination processing method of efficient degradation fluorobenzene phenolic compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5197823A (en) * | 1992-01-08 | 1993-03-30 | Reynolds Metals Company | Method and apparatus for treating PCB-containing soil |
| EP1048327A2 (en) * | 1999-03-29 | 2000-11-02 | Shin-Etsu Chemical Co., Ltd. | Method and agent for reducing chlorinated aromatic compounds |
| CN1539693A (en) * | 2003-10-31 | 2004-10-27 | 中国科学院生态环境研究中心 | Method for dechloridizing organochloric compound |
| CN102166577A (en) * | 2010-12-07 | 2011-08-31 | 清华大学 | Method for destroying chloric persistent organic waste through iron and quartz sand high-energy ball milling |
| CN102909214A (en) * | 2012-10-30 | 2013-02-06 | 中国科学院烟台海岸带研究所 | Combined treatment method of purifying DDT (Dichloro-Diphenyl-Tricgloroethane) heavily-polluted ground soil |
| CN103386314A (en) * | 2013-07-29 | 2013-11-13 | 清华大学 | Method for preparing photocatalyst with visible light response by mechanochemical treatment on polybrominated diphenyl ether solid waste |
| EP2727662A1 (en) * | 2012-10-26 | 2014-05-07 | Biodermol Ambiente S.r.l. | Process for reducing levels of contamination of soils polluted by DDT, DDE, DDD and/or isomers thereof |
-
2017
- 2017-09-27 CN CN201710885380.5A patent/CN107670219B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5197823A (en) * | 1992-01-08 | 1993-03-30 | Reynolds Metals Company | Method and apparatus for treating PCB-containing soil |
| EP1048327A2 (en) * | 1999-03-29 | 2000-11-02 | Shin-Etsu Chemical Co., Ltd. | Method and agent for reducing chlorinated aromatic compounds |
| CN1539693A (en) * | 2003-10-31 | 2004-10-27 | 中国科学院生态环境研究中心 | Method for dechloridizing organochloric compound |
| CN102166577A (en) * | 2010-12-07 | 2011-08-31 | 清华大学 | Method for destroying chloric persistent organic waste through iron and quartz sand high-energy ball milling |
| EP2727662A1 (en) * | 2012-10-26 | 2014-05-07 | Biodermol Ambiente S.r.l. | Process for reducing levels of contamination of soils polluted by DDT, DDE, DDD and/or isomers thereof |
| CN102909214A (en) * | 2012-10-30 | 2013-02-06 | 中国科学院烟台海岸带研究所 | Combined treatment method of purifying DDT (Dichloro-Diphenyl-Tricgloroethane) heavily-polluted ground soil |
| CN103386314A (en) * | 2013-07-29 | 2013-11-13 | 清华大学 | Method for preparing photocatalyst with visible light response by mechanochemical treatment on polybrominated diphenyl ether solid waste |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134201A (en) * | 2018-09-11 | 2019-01-04 | 鲁东大学 | The heterogeneous catalytic hydrogenation defluorination processing method of efficient degradation fluorobenzene phenolic compound |
| CN109134201B (en) * | 2018-09-11 | 2021-09-07 | 鲁东大学 | Heterogeneous catalytic hydrogenation defluorination treatment method for efficiently degrading fluorophenol compounds |
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