CN103495409A - Charcoal-honeycomb ceramic monolithic catalyst as well as preparation and application thereof - Google Patents

Charcoal-honeycomb ceramic monolithic catalyst as well as preparation and application thereof Download PDF

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CN103495409A
CN103495409A CN201310456951.5A CN201310456951A CN103495409A CN 103495409 A CN103495409 A CN 103495409A CN 201310456951 A CN201310456951 A CN 201310456951A CN 103495409 A CN103495409 A CN 103495409A
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honeycomb ceramic
charcoal
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CN103495409B (en
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马磊
张群峰
卢春山
丰枫
李小年
许孝良
江大好
胡文渊
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a charcoal-honeycomb ceramic monolithic catalyst used for performing catalytic dehydrochlorination synthesis of 1,1,2-trichloro ethylene from 1,1,2,2-tetrachloroethane, as well as a preparation and application of the catalyst. The catalyst is prepared by the method comprises the following steps: soaking cordierite honeycomb ceramic which is pre-acidized in resin, taking out and blowing redundant resin away, heating to 50-200 DEG C and performing a curing treatment, and finally performing a carbonizing treatment at a temperature of 400-600 DEG C and in an argon atmosphere, so as to prepare the charcoal-honeycomb ceramic monolithic catalyst. According to the charcoal-honeycomb ceramic (C-HC) monolithic catalyst disclosed by the invention, in the reaction for performing catalytic dehydrochlorination synthesis of the 1,1,2-trichloro ethylene from the 1,1,2,2-tetrachloroethane, compared with the conventional activated charcoal catalyst, the charcoal-honeycomb ceramic (C-HC) monolithic catalyst of a unit charcoal mass has the advantages that the activity is higher, the product, namely, the 1,1,2-trichloro ethylene, is higher in selectivity, the service life of the catalyst is prolonged, and the catalyst is low in recycling cost.

Description

A kind of charcoal-honeycomb ceramic integral formula catalyst and preparation and application thereof
(1) technical field
The present invention relates to a kind of 1,1,2, the highly active active carbon of synthetic 1,1, the 2-trichloro-ethylene of 2-tetrachloroethanes catalysis dechlorination hydrogen-honeycomb ceramic integral formula catalyst, and preparation method thereof with application.
(2) background technology
1,1,2-trichloro-ethylene (1,1,2-trichloroethene, TCE) be a kind of important chemical intermediate, can be used for producing tetrachloro-ethylene, monoxone, dichloroacetyl chloride, Octachlorodipropyl Ether etc., also can be used for extractant, solvent, low temperature conduction oil medium, metal cleaning and fiber and remove the fields such as grease.In recent years, the novel environment-friendly refrigerant HFA 134a (HFC-134a) that the TCE of take is the synthetic replacement fluorine of raw material Leon becomes its main application, makes production capacity and the equal rapid growth of consumption demand amount of TCE.
The synthetic method of TCE mainly contains the de-HCl method of saponification method, pyrolysismethod and gas phase catalysis etc.Saponification method be take acetylene as raw material, and production process can produce a large amount of saponification waste liquids.The pyrolysismethod reaction temperature is high, and power consumption is large, and accessory substance is many.With saponification method, with pyrolysismethod, compare, with 1,1,2,2-tetrachloroethanes (1,1,2,2-tetrachloroethane, TeCA) be raw material, process accessory substance and the three waste discharge of the synthetic TCE of the de-HCl method of gas phase catalysis significantly reduce, and have become the main method of at present synthetic TCE.Active carbon is that the synthetic TCE of the de-HCl of TeCA gas phase catalysis reacts the most frequently used catalyst, but the commercialization active carbon that derives from the natural materials such as shell, timber, coal has the advantages that nature difference is large, impurity content is high, cause activated-carbon catalyst to have the shortcoming of active low, selective not high, poor stability in reaction.
(3) summary of the invention
The object of the present invention is to provide charcoal-ceramic honey comb (C-HC) integral catalyzer of a kind of high activity, high selectivity and high stability, and preparation method thereof with application.
The technical solution used in the present invention is as follows: a kind of for 1, 1, 2, 2-tetrachloroethanes catalysis dechlorination hydrogen synthetic 1, 1, the charcoal of 2-trichloro-ethylene-honeycomb ceramic integral formula catalyst, described charcoal-honeycomb ceramic integral formula catalyst prepares by the following method: the cordierite honeycomb ceramic carrier of acidified processing in advance is immersed in liquid resin, fully after dipping absorption, take out, blow away unnecessary resin, heat 50～200 ℃ and be cured processing, finally under argon gas atmosphere, carry out the charing processing at 400～600 ℃ of temperature, make described charcoal-honeycomb ceramic integral formula catalyst.
Described charcoal-honeycomb ceramic integral formula catalyst preferably prepares by the following method: cordierite honeycomb ceramic carrier is immersed in the acid solution that mass percentage concentration is 1～20%, carry out acidification 1～5h at 30～90 ℃ of temperature, described acid solution is nitric acid, acetic acid, ethanedioic acid, 2,3-dyhydrobutanedioic acid or the benzoic aqueous solution, with extremely neutrality, oven dry of deionized water washing, obtain the cordierite honeycomb ceramic carrier of acidified processing after taking-up; The cordierite honeycomb ceramic carrier of acidified processing is immersed in liquid resin, in 30～80 ℃ of dipping 2～12h, blow away resin unnecessary in duct after taking-up, then under air atmosphere, in 50～200 ℃, solidify 4～12h, finally under argon gas atmosphere, in 400～600 ℃ of charing 2～10h, make described charcoal-honeycomb ceramic integral formula catalyst.
Described cordierite honeycomb ceramic carrier is integrated catalyst carrier commonly used, and profile is generally cylindricality, and cross section is processed as circle, ellipse or square usually.Cordierite honeycomb ceramic carrier is comprised of many parallel ducts vertical with cross section, and the cross section, duct can be circular, square, triangle, hexagon etc.Hole density is generally 30～80 holes/square centimeter.
The cordierite honeycomb ceramic carrier used in the embodiment of the present invention is from Co., Ltd of Yixing Non-Metallic Chemical Mechinery Factory, Jiangsu Prov., cylindrical, diameter 45.8mm, and height 80mm, hole shape is square hole, density 54 holes, hole/cm 2, wall thickness 0.22mm.
Described liquid resin is liquid epoxy resin, phenolic resins, alkyd resins or amino resins, is preferably liquid alkyd resins.
Described acid solution is preferably the aqueous solution of 2,3-dyhydrobutanedioic acid.
The mass percentage concentration of described acid solution is preferably 5～15%.
Highly preferred, described acid solution is 2 of mass percentage concentration 10%, the aqueous solution of 3-dyhydrobutanedioic acid.
Described acidification temperature is 30～90 ℃, preferably 40～80 ℃; The acidification time is 1～5h, preferably 2～4h, more preferably 3～4h.Most preferred, described acidification is at 60 ℃ of lower acidification 4h.
Described impregnation process temperature is 30～80 ℃, and preferably 40～70 ℃, dip time is 2～12h, preferably 4～8h.Most preferred, described impregnation process is at 50 ℃ of lower impregnation process 8h.
Solidification temperature is 50～200 ℃, and preferably 50～150 ℃, be 4～12h, preferably 6～10h hardening time.Most preferred, described solidification temperature is at 100 ℃ of curing 8h.
Carbonization temperature is 400～600 ℃, and preferably 450～550 ℃, carbonization time is 2～10h, preferably 4～8h.Preferred, described charing is in 500 ℃ of charing 6h.
Under argon gas atmosphere, the flow of argon gas is generally 10～100ml/min, preferably 30～80ml/min, more preferably 50ml/min.
Described curing processing is to make the resin on honeycomb ceramic carrier surface fully curing, and it is to make the resin on honeycomb ceramic carrier surface decompose charing that charing is processed,
Comparatively concrete, recommend charcoal of the present invention-honeycomb ceramic integral formula catalyst to prepare by the following method: by cordierite honeycomb ceramic carrier be immersed in mass percentage concentration be 5～15% 2, in the aqueous solution of 3-dyhydrobutanedioic acid, carry out acidification 2～4h at 40～80 ℃, with extremely neutrality, 110～120 ℃ of oven dry of deionized water washing, obtain the monoblock type cordierite honeycomb ceramic of acidified processing after taking-up; The cordierite honeycomb ceramic of acidified processing is immersed in liquid alkyd resins, in 40～70 ℃ of dipping 4～8h, blow away resin unnecessary in duct after taking-up, then under air atmosphere, in 50～150 ℃, solidify 6～10h, last under the argon gas atmosphere of 30～80ml/min, in 450～550 ℃ of charing 4～8h, make described charcoal-honeycomb ceramic integral formula catalyst.
Charcoal provided by the invention-honeycomb ceramic integral formula catalyst can be used for 1,1,2, in synthetic 1,1, the 2-trichloro-ethylene of 2-tetrachloroethanes catalysis dechlorination hydrogen, described method is: with 1,1, and 2, the 2-tetrachloroethanes is raw material, described charcoal-honeycomb ceramic integral formula catalyst packed in fixed bed reactors, and nitrogen buffer gas, under condition of normal pressure, in 150～300 ℃ of reactions, product is through gas-liquid separation, and the gained product liquid is 1,1,2-trichloro-ethylene.
Further, described 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen synthetic 1,1, the method of 2-trichloro-ethylene is preferably: described charcoal-honeycomb ceramic integral formula catalyst packed in fixed bed reactors, and 1,1,2,2-tetrachloroethanes be take the fluid flow of 0.04～0.08ml/min and pass into fixed bed reactors together with the nitrogen that is 40～80ml/min with flow after vaporization, under condition of normal pressure in 200～250 ℃ of reactions, product is through gas-liquid separation, product liquid is 1,1,2-trichloro-ethylene.
Charcoal-ceramic honey comb of the present invention (C-HC) integral catalyzer, 1,1,2, in synthetic 1,1, the 2-trichloro-ethylene reaction of 2-tetrachloroethanes catalysis dechlorination hydrogen, compare with conventional activated-carbon catalyst, have following advantage: 1) charcoal-ceramic honey comb of unit carbonaceous amount (C-HC) integral catalyzer activity is higher; 2) the charcoal layer obtained by resin is free from foreign meter, products therefrom 1,1,2-trichloro-ethylene selectively higher; 3) catalyst longer service life, the recycling cost is low.
(4) accompanying drawing explanation
Cordierite honeycomb ceramic carrier in Fig. 1 embodiment 1 and the charcoal made-honeycomb ceramic integral formula catalyst photo, in figure, A is the cordierite honeycomb ceramic carrier photo, B is charcoal-honeycomb ceramic integral formula catalyst photo.
(5) specific embodiment:
Below with specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Cordierite honeycomb ceramic carrier in embodiment is from Co., Ltd of Yixing Non-Metallic Chemical Mechinery Factory, Jiangsu Prov., cylindrical, diameter 45.8mm, and height 80mm, hole shape is square hole, density 54 holes, hole/cm 2, wall thickness 0.22mm.
Embodiment mono-to six
Embodiment mono-to six has contrasted the impact of the sour kind of acidification on charcoal-ceramic honey comb (C-HC) catalyst performance.Method for preparing catalyst is as follows: cordierite honeycomb ceramic is immersed in to the acid that mass percent concentration is 10% (hydrochloric acid, nitric acid, acetic acid, ethanedioic acid, 2 fully, 3-dyhydrobutanedioic acid, benzoic acid) in solution, in 50 ℃ of processing 3h, after taking-up, by deionized water, wash to neutrality and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 6h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer, the weightening finish of comparing cordierite honeycomb ceramic is the charcoal load capacity, as shown in table 1.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04ml/min, and reaction temperature is 200 ℃, and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 1 below.
Table 1
Figure BDA0000390102240000061
Figure BDA0000390102240000071
Embodiment seven to 13
The impact of the condition that embodiment seven to 13 contrast acidifications process on charcoal-ceramic honey comb (C-HC) catalyst performance.Method for preparing catalyst is as follows: by cordierite honeycomb ceramic be immersed in mass percent concentration be 5～15% 2, in 3-dyhydrobutanedioic acid solution, process 2～4h(in 40～80 ℃ and press table 2 acidification condition), after taking-up, by deionized water, wash to neutrality and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 6h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer, the charcoal load capacity is in Table 2.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04ml/min, and reaction temperature is 200 ℃, and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 2 below.
Table 2
Figure BDA0000390102240000072
Figure BDA0000390102240000081
Embodiment 14 to 20
Embodiment 14 to 20 has contrasted the impact on charcoal-ceramic honey comb (C-HC) catalyst performance of resin kind and immersion condition.Method for preparing catalyst is as follows: by cordierite honeycomb ceramic be immersed in mass percent concentration be 10% 2, in 3-dyhydrobutanedioic acid solution, process 4h in 60 ℃, after taking-up with the deionized water washing to neutral and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in resin (epoxy resin, phenolic resins, alkyd resins, amino resins etc.), in 40～70 ℃ of dipping 4～8h(, presses table 3 immersion condition), blow away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer, the charcoal load capacity is in Table 3.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04ml/min, and reaction temperature is 200 ℃, and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 3 below.
Table 3
Figure BDA0000390102240000091
Embodiment 21 to 24
The impact of embodiment 21 to 24 contrast conditions of cure on charcoal-ceramic honey comb (C-HC) catalyst performance.Method for preparing catalyst is as follows: by cordierite honeycomb ceramic be immersed in mass percent concentration be 10% 2, in 3-dyhydrobutanedioic acid solution, process 4h in 60 ℃, after taking-up with the deionized water washing to neutral and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 8h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace and solidify 6～10h(by table 4 condition of cure in 50～150 ℃ under air atmosphere), make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04ml/min, and reaction temperature is 200 ℃, and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 4 below.
Table 4
Figure BDA0000390102240000101
Embodiment 25 to 30
The impact of embodiment 25 to 34 contrast carbonization conditions on charcoal-ceramic honey comb (C-HC) catalyst performance.Method for preparing catalyst is as follows: by cordierite honeycomb ceramic be immersed in mass percent concentration be 10% 2, in 3-dyhydrobutanedioic acid solution, process 4h in 60 ℃, after taking-up with the deionized water washing to neutral and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 8h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 30～80ml/min at flow, in 450～550 ℃ of charing 4～8h(, press table 5 carbonization condition), make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04ml/min, and reaction temperature is 200 ℃, and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 5 below.
Table 5
Figure BDA0000390102240000111
Embodiment 31 to 36
Embodiment 31 to 36 has contrasted the impact of synthetic 1,1, the 2-trichloro-ethylene reaction condition of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen.Method for preparing catalyst is as follows: by cordierite honeycomb ceramic be immersed in mass percent concentration be 10% 2, in 3-dyhydrobutanedioic acid solution, process 4h in 60 ℃, after taking-up with the deionized water washing to neutral and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 8h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer, the charcoal load capacity is 5.3g.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: charcoal-ceramic honey comb (C-HC) catalyst made in the embodiment that packs in fixed bed reactors, N 2carrier gas flux is 40～80ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.04～0.08ml/min, and reaction temperature is 200～250 ℃ (pressing table 6 catalytic reaction condition), and product is the product liquid gas chromatographic analysis after gas-liquid separation.During reaction 4h, the sample analysis result is as shown in table 6 below.
Table 6
Figure BDA0000390102240000121
Embodiment 37 to 38
Embodiment 37 to 38 has contrasted the catalytic performance of charcoal-ceramic honey comb (C-HC) integral catalyzer and commercialization activated-carbon catalyst.The commercialization activated-carbon catalyst reaches chemical industry Co., Ltd purchased from the sage that becomes civilized, cylindrical, diameter 3mm, length 7～9mm.The preparation method is as follows for charcoal-ceramic honey comb (C-HC) integral catalyzer: by cordierite honeycomb ceramic be immersed in mass percent concentration be 10% 2, in 3-dyhydrobutanedioic acid solution, in 60 ℃ of processing 4h, after taking-up, by deionized water, wash to neutrality and in 110 ℃ of oven dry.Acidified pretreated ceramic honey comb is immersed in alkyd resins, in 50 ℃ of dipping 8h, blows away resin unnecessary in duct after taking-up.Then ceramic honey comb is proceeded to Muffle furnace under air atmosphere in 100 ℃ of curing 8h, make the resin on ceramic honey comb surface fully curing.In the last argon gas atmosphere that is 50ml/min at flow, in 500 ℃ of charing 6h, make the resin on ceramic honey comb surface decompose charing, obtain charcoal-ceramic honey comb (C-HC) integral catalyzer, weightening finish 5.3g, i.e. load carbon 5.3g.
Synthetic 1,1, the 2-trichloro-ethylene course of reaction of 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen is as follows: be respectively charged into charcoal-ceramic honey comb (C-HC) catalyst and activated-carbon catalyst 5.3g that embodiment 37 makes in fixed bed reactors, N 2carrier gas flux is 40ml/min, and 1,1,2,2-tetrachloroethanes flow is 0.06ml/min, and reaction temperature is 200 ℃ (pressing table 7 catalytic reaction condition), and product is the product liquid gas chromatographic analysis after gas-liquid separation.When reaction 1h, 4h, 8h, the sample analysis result is as shown in table 7 below.
Table 7
Figure BDA0000390102240000131
Table 7 result shows, under the circumstances of identical carbon content, the conversion ratio of charcoal-ceramic honey comb (C-HC) integral catalyzer in reaction with selectively all will be higher than activated-carbon catalyst.Simultaneously, it is stable that the catalytic activity of charcoal-ceramic honey comb (C-HC) integral catalyzer keeps within the reaction time, and stability is compared activated-carbon catalyst and significantly improved.

Claims (9)

1. one kind for 1,1,2,2-tetrachloroethanes catalysis dechlorination hydrogen synthetic 1,1, the charcoal of 2-trichloro-ethylene-honeycomb ceramic integral formula catalyst, it is characterized in that described charcoal-honeycomb ceramic integral formula catalyst prepares by the following method: the cordierite honeycomb ceramic of acidified processing in advance is immersed in liquid resin, fully after dipping absorption, take out, blow away unnecessary resin, heat 50～200 ℃ and be cured processing, finally under argon gas atmosphere, carry out the charing processing at 400～600 ℃ of temperature, make described charcoal-honeycomb ceramic integral formula catalyst.
2. charcoal as claimed in claim 1-honeycomb ceramic integral formula catalyst, it is characterized in that described charcoal-honeycomb ceramic integral formula catalyst prepares by the following method: cordierite honeycomb ceramic is immersed in the acid solution that mass percentage concentration is 1～20%, carry out acidification 1～5h at 30～90 ℃ of temperature, described acid solution is nitric acid, acetic acid, ethanedioic acid, 2,3-dyhydrobutanedioic acid or the benzoic aqueous solution, with extremely neutrality, oven dry of deionized water washing, obtain the cordierite honeycomb ceramic of acidified processing after taking-up; The cordierite honeycomb ceramic of acidified processing is immersed in liquid resin, in 30～80 ℃ of dipping 2～12h, blow away resin unnecessary in duct after taking-up, then under air atmosphere, in 50～200 ℃, solidify 4～12h, finally under argon gas atmosphere, in 400～600 ℃ of charing 2～10h, make described charcoal-honeycomb ceramic integral formula catalyst.
3. charcoal as claimed in claim 1 or 2-honeycomb ceramic integral formula catalyst, is characterized in that described liquid resin is liquid epoxy resin, phenolic resins, alkyd resins or amino resins.
4. charcoal as claimed in claim 2-honeycomb ceramic integral formula catalyst, is characterized in that the aqueous solution that described acid solution is 2,3-dyhydrobutanedioic acid.
5. charcoal as claimed in claim 2-honeycomb ceramic integral formula catalyst, the mass percentage concentration that it is characterized in that described acid solution is 5～15%.
6. charcoal as claimed in claim 3-honeycomb ceramic integral formula catalyst, is characterized in that described liquid resin is liquid alkyd resins.
7. charcoal as claimed in claim 2-honeycomb ceramic integral formula catalyst, it is characterized in that described charcoal-honeycomb ceramic integral formula catalyst prepares by the following method: by cordierite honeycomb ceramic be immersed in mass percentage concentration be 5～15% 2, in the aqueous solution of 3-dyhydrobutanedioic acid, carry out acidification 2～4h at 40～80 ℃, with extremely neutrality, 110～120 ℃ of oven dry of deionized water washing, obtain the cordierite honeycomb ceramic of acidified processing after taking-up; The cordierite honeycomb ceramic of acidified processing is immersed in liquid alkyd resins, in 40～70 ℃ of dipping 4～8h, blow away resin unnecessary in duct after taking-up, then under air atmosphere, in 50～150 ℃, solidify 6～10h, last under the argon gas atmosphere of 30～80ml/min, in 450～550 ℃ of charing 4～8h, make described charcoal-honeycomb ceramic integral formula catalyst.
8. charcoal as described as one of claim 1～7-honeycomb ceramic integral formula catalyst is for 1,1,2, the method of synthetic 1,1, the 2-trichloro-ethylene of 2-tetrachloroethanes catalysis dechlorination hydrogen, it is characterized in that described method is: with 1,1,2, the 2-tetrachloroethanes is raw material, described charcoal-honeycomb ceramic integral formula catalyst packed in fixed bed reactors, and nitrogen buffer gas, under condition of normal pressure, in 150～300 ℃ of reactions, product is through gas-liquid separation, and the gained product liquid is 1,1,2-trichloro-ethylene.
9. method as claimed in claim 8, it is characterized in that described method is: described charcoal-honeycomb ceramic integral formula catalyst is packed in fixed bed reactors, 1,1,2, the 2-tetrachloroethanes be take the fluid flow of 0.04～0.08ml/min and pass into fixed bed reactors together with the nitrogen that is 40～80ml/min with flow after vaporization, under condition of normal pressure, in 200～250 ℃ of reactions, product is through gas-liquid separation, and product liquid is 1,1,2-trichloro-ethylene.
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CN107199039A (en) * 2017-06-29 2017-09-26 浙江工业大学 A kind of metallic nickel insertion porous charcoal coating ceramic honey comb integral catalyzer and application
CN109926081A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene
CN110433808A (en) * 2019-07-02 2019-11-12 浙江工业大学 Metal-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst and preparation method and application thereof
CN115845919A (en) * 2022-11-23 2023-03-28 浙江工业大学 Nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107199039A (en) * 2017-06-29 2017-09-26 浙江工业大学 A kind of metallic nickel insertion porous charcoal coating ceramic honey comb integral catalyzer and application
CN107199039B (en) * 2017-06-29 2020-04-21 浙江工业大学 Metallic nickel embedded porous carbon coated honeycomb ceramic monolithic catalyst and application thereof
CN109926081A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene
CN110433808A (en) * 2019-07-02 2019-11-12 浙江工业大学 Metal-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst and preparation method and application thereof
CN110433808B (en) * 2019-07-02 2022-06-21 浙江工业大学 Metal-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst and preparation method and application thereof
CN115845919A (en) * 2022-11-23 2023-03-28 浙江工业大学 Nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst

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