CN106140139B - A kind of catalyst for hydrogen peroxide decomposition and application method - Google Patents
A kind of catalyst for hydrogen peroxide decomposition and application method Download PDFInfo
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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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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 60
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 50
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- -1 VIB group metal oxides Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
- 229910000423 chromium oxide Inorganic materials 0.000 claims 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 claims 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 102000040350 B family Human genes 0.000 abstract description 9
- 108091072128 B family Proteins 0.000 abstract description 9
- 238000004821 distillation Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 26
- 238000010494 dissociation reaction Methods 0.000 description 9
- 208000018459 dissociative disease Diseases 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- AQRDGTBNWBTFKJ-UHFFFAOYSA-N molybdenum;dihydrate Chemical compound O.O.[Mo] AQRDGTBNWBTFKJ-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910002458 Co-SiO2 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 1
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- ZPIZRHAHXTZZPJ-UHFFFAOYSA-N methanol;propane Chemical compound OC.CCC ZPIZRHAHXTZZPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Epoxy Compounds (AREA)
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
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)
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| 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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| CN101077984A (en) * | 2007-07-25 | 2007-11-28 | 中国石油大学(北京) | Deep desulfurization method for liquefied petroleum gas |
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