CN106140139B - A kind of catalyst and application method decomposed for hydrogen peroxide - Google Patents

A kind of catalyst and application method decomposed for hydrogen peroxide Download PDF

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CN106140139B
CN106140139B CN201510191155.2A CN201510191155A CN106140139B CN 106140139 B CN106140139 B CN 106140139B CN 201510191155 A CN201510191155 A CN 201510191155A CN 106140139 B CN106140139 B CN 106140139B
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hydrogen peroxide
mass
catalyst
oxide
reaction product
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CN106140139A (en
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张永强
刘易
杜泽学
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A kind of hydrogen peroxide decomposition catalyst, it is characterised in that IV B family metal oxide of VI B family metal oxide, 1-20 mass % containing 1-30 mass % and the III A family metal oxide of 50-98 mass %.Using the decomposition method of hydrogen peroxide in the chlorallylene and hydrogen dioxide epoxidation reaction product of catalyst of the present invention, most of hydrogen peroxide remaining in reaction product can be decomposed before distillation separation, it effectively eliminates higher content of hydrogen peroxide in epoxidation reaction product and the safety of chlorallylene and hydrogen dioxide epoxidation reaction production epoxychloropropane is improved to the potential hazard of subsequent distillation separation process.

Description

A kind of catalyst and application method decomposed for hydrogen peroxide
Technical field
The present invention relates to a kind of hydrogen peroxide decomposition catalyst and its application, more specifically to a kind of hydrogen peroxide point Solve the decomposition application of catalyst and the catalyst for hydrogen peroxide in chlorallylene and hydrogen dioxide epoxidation reaction product.
Background technique
Hydrogen peroxide is a kind of oxidant of green, such as USP4, disclosed in 833,260, in titanium-silicon molecular sieve catalyst It, can efficiently and cleanly synthesizing epoxy chlorine by chlorallylene and hydrogen dioxide epoxidation reaction in the presence of solvent methanol Propane.And epoxychloropropane is a kind of important basic organic chemical industry raw material and intermediate, be widely used in synthetic epoxy resin, A variety of industrial products such as chlorohydrin rubber, drug, pesticide, surfactant and plasticizer.
CN101747296A and CN101747297A are further disclosed by chlorallylene and hydrogen dioxide epoxidation reaction The method for producing epoxychloropropane, the high conversion rate realized in hydrogen peroxide are higher than in the selectivity of 97% and epoxychloropropane Long-time continuous stable ground synthesizing epoxy chloropropane in the case where 95%.But during long time running, hydrogen peroxide Conversion ratio is usually maintained between 97-99%, so that the hydrogen peroxide containing 0.05-0.5 mass % in epoxidation reaction product. The epoxidation reaction product of hydrogen peroxide containing 0.05-0.5 mass % is in subsequent distillation separation process, due to peroxidating The boiling point (151.4 DEG C) of hydrogen is relatively high, is easily collected on the positions such as the higher tower reactor of temperature, and during heating, peroxidating Hydrogen be possible to be formed with organic matter the organic peroxide for being easy explosion or itself decompose release oxygen and with have Machine object steam forms explosive mixture, is a kind of latent dangerous factor for threatening safety in production, to epoxidation reaction product It needs to be eliminated before carrying out distillation separation.
Hydrogen peroxide in low concentration hydrogen peroxide aqueous solution (content of hydrogen peroxide is between 0.05-5 mass %) is divided Solution, (Co-SiO of hydrogen peroxide is catalytically decomposed in Yuan Qiang, Li Hui, Wu Yingqiu, Yang Lefu, efficient cryogenic to Yuan Qiang et al.2Catalyst, Xiamen University's journal (natural science edition), 49 (4), 2010,589-592) it reports using sol-gal process synthesis M-SiO2(M =Ni, Zn, Fe, Bi, Cu, Al, Cd, Co) catalyst, peroxynitrite decomposition hydrogen content is the peroxidating of 3.4 mass % at 20 DEG C Aqueous solution of hydrogen, wherein Co-SiO2The content of hydrogen peroxide can be reduced to 0.20 mass % in 30min by catalyst, be shown The catalytic activity more much higher than other catalyst.Suzan A.Ali(Suzan A.Ali,Effect of Sequence of Impregnation on the Structure and Catalytic Properties of Cu-Co-Al-Oxide System.J.Mater.Sci.Technol., Vol.20, No.1,2004,55-58) report, using the oxidation of alumina load Cobalt-copper oxide catalyst, peroxynitrite decomposition hydrogen content is the aqueous hydrogen peroxide solution of 0.73 mass % at 30 DEG C, but does not give Specific hydrogen peroxide conversion data out.
To residual hydrogen peroxide in alkene and hydrogen dioxide epoxidation reaction product (content of hydrogen peroxide is lower than 1 mass %) Decomposition, Chinese patent ZL01814048.3 and USP7,138,534 disclose a kind of method for continuous production of propylene oxide, right The epoxidation product of propylene and hydrogen peroxide is first sent into destilling tower from removed overhead propylene and propylene oxide, then will contain first The destilling tower tower bottom discharging of alcohol, water, epoxidation reaction by-product and hydrogen peroxide, which is sent into, is equipped with group VIII metal or metal oxygen In the fixed bed reactors of compound catalyst, the peroxynitrite decomposition hydrogen in the case where temperature is 80-90 DEG C and alkaline condition, but do not provide Specific catalyst composition.
In conclusion for comprising alkene, epoxyalkane, reaction dissolvent, water and epoxidation reaction by-product epoxidation Reaction product, there has been no the open reports for directly decomposing hydrogen peroxide therein.
Summary of the invention
One of the objects of the present invention is to provide a kind of catalyst for peroxynitrite decomposition hydrogen, the second purpose is to provide this The decomposition method of catalyst hydrogen peroxide in chlorallylene and hydrogen dioxide epoxidation reaction product.
A kind of catalyst for peroxynitrite decomposition hydrogen, it is characterised in that the VI B race metal oxidation containing 1-30 mass % III A family metal oxide of object, the IV B family metal oxide of 1-20 mass % and 50-98 mass %.
It is a kind of comprising alkene, epoxyalkane epoxidation reaction product in hydrogen peroxide decomposition method, feature exists It is carried out in the presence of hydrogen peroxide decomposition catalyst in aforementioned present invention.
The decomposition method of hydrogen peroxide in a kind of chlorallylene and hydrogen dioxide epoxidation reaction product, comprising: a) will be from The epoxidation reaction product that epoxidation reactor comes out is introduced into hydrogen peroxide dissociation reaction device, with hydrogen peroxide decomposition catalyst It is contacted at 0-50 DEG C, most of hydrogen peroxide therein is made to be decomposed into oxygen and water;B) by hydrogen peroxide dissociation reaction device Discharging is sent into gas-liquid separator together after mixing with optional inert gas, removes incoagulable gas therein, feature exists Contain the VI B family metal oxide of 1-30 mass %, the IV B metal oxide of 1-20 mass % in hydrogen peroxide decomposition catalyst With the III A family metal oxide of 50-98 mass %.
Method provided by the invention, to including chlorallylene, epoxychloropropane, reaction dissolvent, water, epoxidation reaction by-product The epoxidation reaction product of object and hydrogen peroxide, directly decomposes hydrogen peroxide therein, with eliminate in epoxidation reaction product compared with The hydrogen peroxide of high-content distills isolated potential hazard to epoxidation reaction product, improves chlorallylene and hydrogen peroxide epoxy Change the safety of reaction production epoxychloropropane.
Specific embodiment
A kind of catalyst decomposed for hydrogen peroxide, it is characterised in that the VI B race metal oxidation containing 1-30 mass % III A family metal oxide of object, the IV B family metal oxide of 1-20 mass % and 50-98 mass %.
Preferably, catalyst provided by the invention, VI B family metal oxide, 1-10 mass % containing 2-20 mass % IV B family metal oxide and 70-97 mass % III A family metal oxide.
In described catalyst, the VI B family metal oxide is the oxide of crome metal, molybdenum and tungsten, preferably chromium With the oxide of molybdenum;The IV B metal oxide is the oxide of titanium, zirconium and hafnium, the preferably oxide of titanium and zirconium;It is described III A family metal oxide be metallic aluminium, gallium, indium and thallium oxide, the preferably oxide of aluminium.
It is furthermore preferred that hydrogen peroxide decomposition catalyst of the invention contains 2-10 mass % chromated oxide, 2-10 mass % Molybdenum oxide, 2-10 mass % Zirconium oxide and 70-94 mass % aluminium oxide.
The preparation method of the hydrogen peroxide decomposition catalyst include: 1) by III A family metal oxide or hydroxide, Acidic aluminum sol, organic matter extrusion aid, organic matter pore-foaming agent and paste making agent are sufficiently kneaded into wet plastic body, then extruded moulding For wet strip shape body;2) wet strip shape body obtains catalyst carrier by dry and roasting;3) with VI B race metal salt solution and IV B metal salt solution impregnated catalyst support obtains catalyst by dry and roasting.
The III A family metal oxide is aluminium oxide, and metal hydroxides is aluminium hydroxide.
In the step 1) of the preparation method of the catalyst, the III A family metal oxide or hydroxide, acidity The mass ratio of the dosage of Aluminum sol, organic matter extrusion aid, organic matter pore-foaming agent and paste making agent is 100: (50-200): (1-100): (1-25)∶(1-60)。
In the step 2) of the preparation method of the catalyst, the drying temperature is 0-120 DEG C, drying time 1- 48h;The maturing temperature is 400-800 DEG C, calcining time 1-48h.
The content of aluminium oxide is 1-25 mass %, preferably 10-25 mass % in the acidic aluminum sol.
The organic matter extrusion aid is in starch, carboxymethyl cellulose, hydroxyethyl cellulose, citric acid and sesbania powder One or several kinds, preferably one of starch, citric acid and sesbania powder or several.
The organic matter pore-foaming agent be selected from one of polyethylene glycol, polypropylene glycol and alkyl phenol polyoxyethylene ether or It is several, preferably polypropylene glycol and alkyl phenol polyoxyethylene ether.
The metal salt solution is metal nitrate, the aqueous solution of metal carboxylate and metal acid-salt, alcoholic solution and ketone One of solution is several, preferably in the aqueous solution and alcoholic solution of metal nitrate, metal carboxylate and metal acid-salt One kind.
The paste making agent is one of ketone of pure and mild C3-C4 of dust technology, water, C1-C4 or several, preferably dilute One of nitric acid, water, methanol, ethyl alcohol, isopropanol and acetone are several, further preferably dust technology and water.
The content of nitric acid is 0.1-20 mass %, preferably 1-10 mass % in the dust technology.
In the step 3) of the preparation method of the catalyst, the dipping temperature of the metal salt solution is 0-50 DEG C, Time is 1-48h;The drying temperature is 50-120 DEG C, drying time 1-48h;The maturing temperature is 300-700 DEG C, calcining time 1-48h.
The present invention also provides it is a kind of comprising alkene, epoxyalkane epoxidation reaction product in hydrogen peroxide decomposition Method, it is characterised in that carried out in the presence of the hydrogen peroxide decomposition catalyst of aforementioned present invention.
The present invention still further provides hydrogen peroxide in a kind of chlorallylene and hydrogen dioxide epoxidation reaction product Decomposition method, comprising: a) the epoxidation reaction product come out from epoxidation reactor is introduced into hydrogen peroxide dissociation reaction device, It is contacted at 0-50 DEG C with hydrogen peroxide decomposition catalyst, most of hydrogen peroxide therein is made to be decomposed into oxygen and water;B) will The discharging of hydrogen peroxide dissociation reaction device is sent into gas-liquid separator together after mixing with optional inert gas, is removed therein Incoagulable gas, it is characterised in that hydrogen peroxide decomposition catalyst contains the VI B family metal oxide of 1-30 mass %, 1-20 matter Measure the IV B metal oxide of % and the III A family metal oxide of 50-98 mass %.
The content of hydrogen peroxide is 0.05-1.0 matter in the chlorallylene and hydrogen dioxide epoxidation reaction product Measure %, preferably 0.05-0.6 mass %.
The temperature that the hydrogen peroxide decomposes is 0-50 DEG C, preferably 10-40 DEG C.
The pressure that the hydrogen peroxide decomposes is 0.1-2.0MPa, preferably 0.1-1.0MPa.
When the hydrogen peroxide decomposition catalyst disperses in the reactor with liquid motion, the dosage of catalyst is ring The 0.1-40% of oxidation reaction product quality, reaction time 0.01-24h, the preferably dosage of catalyst are epoxidation reaction The 1-20% of product quality, reaction time 0.1-10h.
When the hydrogen peroxide decomposition catalyst it is fixed in the reactor when, the matter when feeding liquid of epoxidation reaction product Amount air speed is 0.01-20h-1, preferably 0.1-10h-1
It, can be by major part remaining in chlorallylene and hydrogen dioxide epoxidation reaction product using method of the invention Hydrogen peroxide is decomposed before distillation separates epoxidation reaction product, effectively eliminates higher mistake in epoxidation reaction product Hydrogen content is aoxidized to the potential hazard of subsequent distillation separation process, chlorallylene is improved and hydrogen dioxide epoxidation reaction produces ring The safety of oxygen chloropropane.Since the decomposition temperature of hydrogen peroxide is low, in hydrogen peroxide decomposable process middle ring oxidation reaction product Epoxychloropropane decomposition loss can be ignored, remain epoxidation reaction product middle ring oxidation chloropropane high selection Property.
It is possible can both to have eliminated high level hydrogen peroxide in epoxidation reaction product for method provided by the invention Potential safety hazard, and can guarantee the highly selective of epoxychloropropane in epoxidation reaction product, meet wanting for industrial application It asks, and technical process is simple, it is easy to accomplish.
The following examples will be further described method of the invention, but not thereby limiting the invention.
Embodiment 1
By 300.00 grams of aluminium hydroxide powders, (alumina content 68.2%, photoinitiator chemical Co., Ltd, Shandong Zibo Thailand are raw Produce), 75.00 grams of starch (analytical reagents), 15.00 grams of sesbania powders (production of Henan Lankao natural plant gum factory), 415.0 grams of aluminium oxide Content be 22.4% Aluminum sol (production of Hunan Jian Chang petrochemical industry limited liability company), 25.00 grams of octylphenol polyethylene ethylene oxides (15) ether (OP-15, the production of Xingtai Ke Wang auxiliary chemicals Co., Ltd) and 60.00 grams of nitric acid contents are 3.0 mass %'s Dust technology is sufficiently mediated in multifunction catalyst molding machine (production of South China Science & Engineering University's science and technology industry head factory) and obtains wet modeling Property body, then extruded moulding be φ 1.2mm filled circles column, be put into chamber type electric resistance furnace after 24 hours are dried at 20-25 DEG C In, 120 DEG C are heated to from 20 DEG C of heating rates with 3 DEG C/min and is stopped 3 hours, are then added with the heating rate of 5 DEG C/min Heat is to 600 DEG C and stops 20 hours, and cylindrical bars catalyst carrier A is obtained after natural cooling.
Embodiment 2
By 317.80 grams of aluminium hydroxide powders, (alumina content 74.2%, photoinitiator chemical Co., Ltd, Shandong Zibo Thailand are raw Produce), 7.50 grams of sesbania powders (production of Henan Lankao natural plant gum factory), 334.82 grams of alumina contents for 22.4% Aluminum sol (lake Nan Jianchang petrochemical industry limited liability company production), 15.00 grams of octylphenol polyethylene ethylene oxide (15) ethers (OP-15, Xingtai sections The production of king's auxiliary chemicals Co., Ltd) and 75.00 grams of deionized waters in multifunction catalyst molding machine, (South China Science & Engineering University is scientific and technological Industry head factory production) in sufficiently mediate obtain wet plastic body, then extruded moulding be φ 1.2mm filled circles column, 15 It is put into chamber type electric resistance furnace after drying 18 hours at DEG C, is heated to 120 DEG C from 20 DEG C of heating rates with 5 DEG C/min and stops 5 Hour, 550 DEG C then are heated to the heating rate of 3 DEG C/min and is stopped 15 hours, and cylindrical bars catalysis is obtained after natural cooling Agent carrier B.
Embodiment 3
At 24 DEG C, 5.70 grams of molybdate dihydrate acid ammoniums, 8.54 gram of nine water chromic nitrate and 5.35 gram of two water zirconyl nitrate are dissolved in It is configured to mixed solution in 45.00 grams of deionized waters, 20.00g stripe shape catalyst carrier A is impregnated into wherein 36h, then at 60 DEG C Baking oven in dry 18h, finally roasted in 450 DEG C of air and obtain metal oxide catalyst afterwards for 24 hours, chromium in catalyst Oxide, the oxide of molybdenum, the oxide of zirconium and aluminium oxide content be respectively 9.00 mass %, 9.00 mass %, 9.00 matter Measure % and 73.00 mass %.
The catalytically active assessment of catalyst carries out in stirred tank reactor, under 35 DEG C and self-generated pressure (0.1MPa), The epoxidation reaction product that 100.00 grams of content of hydrogen peroxide are 0.351 mass % is added in the catalyst of 5.00 grams of long 3-5mm In, it opens stirring and carries out decomposition reaction, take fluid sample in given time interval.
According to method disclosed in CN101747296A, hydrogen peroxide and epoxychloropropane in epoxidation reaction product are analyzed Mass fraction.
The decomposition result of hydrogen peroxide is shown in Table 1, w thereinHPOIndicate the mass fraction of hydrogen peroxide, wECHIndicate epoxy chlorine The mass fraction of propane, XHPOIndicate the conversion ratio of hydrogen peroxide, XECHIndicate the resolution ratio of epoxychloropropane.
Table 1
Reaction time/h wHPO/ % wECH/ % XHPO/ % XECH/ %
0 0.351 12.91 0 0
1.0 0.009 12.92 97.44 -0.08
Embodiment 4
At 20 DEG C, 4.57 grams of molybdate dihydrate acid ammoniums, 6.85 gram of nine water chromic nitrate and 4.29 gram of two water zirconyl nitrate are dissolved in It is configured to mixed solution in 105.00 grams of deionized waters, 60.00g stripe shape catalyst carrier B is impregnated into wherein 30h, then at 90 DEG C Under baking oven in dry 8h, obtain metal oxide catalyst, chromium in catalyst after finally roasting 20h in 550 DEG C of air Oxide, the oxide of molybdenum, the oxide of zirconium and aluminium oxide content be respectively 3.00 mass %, 3.00 mass %, 3.00 Quality % and 91.00 mass %.
According to the decomposition for carrying out hydrogen peroxide in epoxidation reaction product with the identical method of embodiment 3, except that: The catalytically active assessment of catalyst carries out in fixed bed jacketed pipe type reactor, pressure 0.5MPa, temperature are 35 DEG C, epoxy Mass space velocity is 1.02h when changing the feeding liquid of reaction product-1, the content of hydrogen peroxide is 0.395 matter in epoxidation reaction product Measure %.
The decomposition result of hydrogen peroxide is shown in Table 2, w thereinHPO1And wHPO2Respectively indicate the charging of hydrogen peroxide dissociation reaction device With the mass fraction of hydrogen peroxide in discharging, wECH1And wECH2Respectively indicate the charging of hydrogen peroxide dissociation reaction device and discharging middle ring The mass fraction of oxygen chloropropane.
Table 2
Feed time/h wHPO1/ % wHPO2/ % wECH1/ % wECH2/ % XHPO/ % XECH/ %
24 0.395 0.028 14.57 14.50 92.91 0.48
Embodiment 5
At 12 DEG C, 1.52 grams of molybdate dihydrate acid ammoniums, 2.66 gram of nine water chromic nitrate and 1.19 gram of two water zirconyl nitrate are dissolved in It is configured to mixed solution in 35.00 grams of deionized waters, wherein for 24 hours by 20.00g stripe shape catalyst carrier B dipping, then at 80 DEG C Baking oven in dry 12h, obtain metal oxide catalyst after finally roasting 12h in 400 DEG C of air, chromium in catalyst Oxide, the oxide of molybdenum, the oxide of zirconium and aluminium oxide content be respectively 3.50 mass %, 3.00 mass %, 2.50 matter Measure % and 91.00 mass %.
Using the decomposition for carrying out hydrogen peroxide in epoxidation reaction product with the identical method of embodiment 3, except that: The quality of catalyst is 3.00 grams, decomposition temperature is 25 DEG C, the content of hydrogen peroxide is 0.185 matter in epoxidation reaction product Measure %.
The decomposition result of hydrogen peroxide is shown in Table 3.
Table 3
Reaction time/h wHPO/ % wECH/ % XHPO/ % XECH/ %
0 0.185 12.68 0 0
1.0 0.030 12.62 83.78 0.47
Comparative example 1
Using point for preparing hydrogen peroxide in catalyst and progress epoxidation reaction product with the identical method of embodiment 3 Solution, except that: hydrogen peroxide dissociation reaction is carried out in the case where temperature is 80 DEG C and self-generated pressure is 0.5MPa, hydrogen peroxide Decomposition result is shown in Table 4.
Table 4
Reaction time/h wHPO/ % wECH/ % XHPO/ % XECH/ %
0 0.351 12.91 0 0
1.0 0.006 12.19 98.29 5.58
Comparative example 2
Using point for preparing hydrogen peroxide in catalyst and progress epoxidation reaction product with the identical method of embodiment 4 Solution, except that: hydrogen peroxide dissociation reaction is carried out in the case where temperature is 80 DEG C and pressure is 0.8MPa, the decomposition of hydrogen peroxide It the results are shown in Table 5.
Table 5
Feed time/h wHPO1/ % wHPO2/ % wECH1/ % wECH2/ % XHPO/ % XECH/ %
24 0.395 0.005 14.57 12.27 98.73 15.79
Comparative example 3
Using point for preparing hydrogen peroxide in catalyst and progress epoxidation reaction product with the identical method of embodiment 5 Solution, except that: hydrogen peroxide dissociation reaction is carried out in the case where temperature is 65 DEG C and self-generated pressure is 0.2MPa, hydrogen peroxide Decomposition result is shown in Table 6.
Table 6
Reaction time/h wHPO/ % wECH/ % XHPO/ % XECH/ %
0 0.185 12.68 0 0
1.0 0.009 11.98 95.14 5.52
The result decomposed from above-mentioned hydrogen peroxide can be seen that using method of the invention, not only can be anti-by epoxidation It answers in product 83% or more hydrogen peroxide to be decomposed into oxygen and water, keeps the content of hydrogen peroxide in epoxidation reaction product not high In 0.03%, and in epoxidation reaction product, the resolution ratio of epoxychloropropane is respectively less than 0.5%, and the content of epoxychloropropane exists Hydrogen peroxide decomposes front and back and varies less, and maintains the highly selective of epoxychloropropane in epoxidation reaction product.And use pair The method of ratio, although can also make the content of hydrogen peroxide in epoxidation reaction product not higher than 0.03%, epoxidation The resolution ratio of epoxychloropropane is both greater than 5% in reaction product, and the content of epoxychloropropane declines significantly, will reduce significantly The selectivity of epoxychloropropane in epoxidation reaction product.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (8)

1. a kind of catalyst decomposed for hydrogen peroxide in chlorallylene and hydrogen dioxide epoxidation reaction product, feature exist In the VI B family metal oxide containing 1-30 mass %, the IV B family metal oxide of 1-20 mass % and 50-98 mass % III A family metal oxide, wherein the VI B family metal oxide is the oxide of crome metal and the oxide of metal molybdenum, institute The IV B family metal oxide stated is the oxide of zirconium, and the III A family metal oxide is the oxide of metallic aluminium.
2. according to the catalyst of claim 1, it is characterised in that contain the VI B family metal oxide of 2-20 mass %, 1-10 matter Measure the IV B family metal oxide of % and the III A family metal oxide of 70-97 mass %.
3. according to the catalyst of claim 1, the oxidation of the oxide, the molybdenum of 2-10 mass % of the chromium containing 2-10 mass % Object, 2-10 mass % zirconium oxide and 70-94 mass % aluminium oxide.
4. the decomposition method of hydrogen peroxide in a kind of chlorallylene and hydrogen dioxide epoxidation reaction product, comprising: a) will be from ring The epoxidation reaction product that oxidation reactor comes out is introduced into hydrogen peroxide dissociation reaction device, is existed with hydrogen peroxide decomposition catalyst It is contacted at 0-50 DEG C, most of hydrogen peroxide therein is made to be decomposed into oxygen and water;B) going out hydrogen peroxide dissociation reaction device Material is sent into gas-liquid separator together after mixing with optional inert gas, removes incoagulable gas therein, it is characterised in that Described hydrogen peroxide decomposition catalyst is the catalyst of one of claim 1-3.
5. according to method for claim 4, wherein the content of hydrogen peroxide in the epoxidation reaction product is 0.05-1.0 Quality %.
6. according to method for claim 4, wherein the pressure that the hydrogen peroxide decomposes is 0.1-2.0MPa.
7. according to method for claim 4, it is characterised in that the catalyst be dispersed in hydrogen peroxide dissociation reaction device with Liquid flowing, the dosage of catalyst are the 0.1-40%, reaction time 0.01-24h of epoxidation reaction product quality.
8. according to method for claim 4, it is characterised in that carried out in fixed bed, the matter when feeding liquid of epoxidation reaction product Amount air speed is 0.01-20h-1
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CN109293600B (en) * 2018-11-12 2020-11-06 江苏扬农化工集团有限公司 Method for removing residual hydrogen peroxide in epoxy chloropropane oil layer
CN111774064B (en) * 2019-04-04 2023-04-11 中国石油化工股份有限公司 Catalyst for decomposing hydrogen peroxide in epoxidation reaction product of 3-chloropropene and hydrogen peroxide
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