CN110090666A - A method of improving the heteropolyacid catalyst rate of recovery - Google Patents
A method of improving the heteropolyacid catalyst rate of recovery Download PDFInfo
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- CN110090666A CN110090666A CN201910474851.2A CN201910474851A CN110090666A CN 110090666 A CN110090666 A CN 110090666A CN 201910474851 A CN201910474851 A CN 201910474851A CN 110090666 A CN110090666 A CN 110090666A
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- Prior art keywords
- catalyst
- recovery yield
- catalyst recovery
- heteropolyacid catalyst
- phosphorus tungsten
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003822 epoxy resin Substances 0.000 abstract description 7
- 229920000647 polyepoxide Polymers 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000011026 diafiltration Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Abstract
The invention belongs to industrial catalysis technical fields, and in particular to a method of catalysis epoxidation catalyst recovery yield is improved, a kind of method that raising catalysis epoxidation prepares epoxy resin key intermediate epoxychloropropane catalyst recovery yield is more particularly to.To achieve the object of the present invention, the present invention is with the following method: a kind of phosphorus tungsten/molybdenum heteropolyacid catalyst preparing epoxy resin key intermediate epoxychloropropane for catalysis epoxidation, the method of catalyst recovery yield is improved in removal process, it is to be cooled to certain temperature rapidly after epoxidation reaction, a certain amount of additive is then added into reaction solution, and after stirring a period of time, product is centrifuged, and catalyst is recycled, and improves catalyst recovery yield.
Description
Technical field
The invention belongs to industrial catalysis technical fields, and in particular to a kind of to improve catalysis epoxidation catalyst recovery yield
Method, is more particularly to a kind of raising catalysis epoxidation and prepares epoxy resin key intermediate epoxychloropropane to be recycled with catalyst
The method of rate.
Background technique
Heteropoly acid is by hetero atom (such as P, Si, Fe and Co) and polyatom (such as Mo, W, V, Nb and Ta) by certain
The oxygen-containing polyacid of one kind that structure is made up of oxygen atom ligand bridging.It not only has acidity, and has oxidation-reduction quality, is
A kind of multifunctional novel catalyst；It can be used for being catalyzed the reaction such as homogeneous, heterogeneous and phase transfer.Such catalyst stability
Good, no pollution to the environment is a kind of coming green catalyst.
CN102744088 discloses a kind of precipitation process catalyst particle size regulation method, is to heteropolyacid catalyst, peroxide
Changing hydrogen is that the catalyst particle size that oxidant carries out in epoxidation reaction of olefines catalyst precipitation process is regulated and controled, by inorganic
Salt regulator and reaction condition control, increase, catalyst recovery yield is improved extremely by 88.8% so that catalyst particle size is precipitated
99.9%.Wherein inorganic salts anion part is selected from salt acid group, sulfate radical, acetate, carbonate, phosphate radical, hydrogen phosphate, sulphur
One of sour hydrogen radical and bicarbonate radical, inorganic salts zwitterion part are selected from H+、K+、Na+And NH4 +One of.
Heteropolyacid catalyst is prepared in epoxy resin key intermediate epoxychloropropane industrialization process in catalysis epoxidation,
The lesser partial catalyst of particle is very easy to diafiltration into follow-up separation process during industrialization production, therefore, reaction
Catalyst recovery yield afterwards is most important.On the one hand the loss of catalyst causes the use cost of catalyst, on the other hand may be used
The safety of follow-up separation process can be will affect.Therefore, it after heteropolyacid catalyst catalytic epoxidation, needs to improve back
The granularity of catalyst is received, catalyst loss is reduced, eliminating catalyst influences follow-up separation process.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the object of the present invention is to provide a kind of preparations of raising catalysis epoxidation
The method of epoxy resin key intermediate epoxychloropropane catalyst recovery yield.
To achieve the object of the present invention, the present invention is with the following method:
A kind of phosphorus tungsten/molybdenum heteropolyacid catalysis preparing epoxy resin key intermediate epoxychloropropane for catalysis epoxidation
Agent (preparation method is identical as PCT/CN2019/080417) improves the method for catalyst recovery yield in removal process.It is in ring
After oxidation reaction, it is cooled to certain temperature rapidly, a certain amount of additive is then added into reaction solution, and stir one
After the section time, product is centrifuged, and recycles catalyst, improves catalyst recovery yield.
It is of the present invention be cooled to rapidly certain temperature be 0~35 DEG C, preferably 15~30 DEG C；
Additive of the present invention is one of phosphate, silicate, sulfate, borate and metal oxide etc.
Or several combination；Salt is phosphoric acid, potassium phosphate, sodium phosphate, sodium metasilicate, sulfuric acid, potassium sulfate, sodium sulphate, ammonium sulfate, Boratex
One of, metal oxide is aluminum oxide, silica.
Additive amount of the present invention is the 0.5~20wt%, preferably 5~15wt% for putting into catalyst amount；
Mixing time of the present invention is 5~60min, preferably 15~30min.
Do not carry out improve recycling catalyst particle size at 0.1~110 micron, the more difficult recycling in commercial process,
Catalyst recovery yield is low, and there are security risks into follow-up separation process for diafiltration.The technical solution used through the invention improves
The catalyst that epoxy resin key intermediate epoxychloropropane is prepared for catalysis epoxidation, improves catalyst in removal process
Granularity, recycling catalyst particle size are distributed between 20~250 microns, wherein having there are about 90wt% catalyst particle size is 90
Between~150 microns, catalyst recovery yield >=99.5%.
Specific embodiment
The preparation and application of this catalyst is specifically described in the following examples.Embodiment is not intended to of the invention
Usage range is limited in the condition of embodiment narration.
Embodiment 1
Chloropropene 309.0g and phosphorus heteropoly tungstic acid catalyzer 15g is put into 500mL four-hole boiling flask, is warming up to reflux,
It is added dropwise 49.1% hydrogen peroxide 69.6g under stirring in 2h, the reaction was continued under reflux temperature 3h；Reaction was completed that material is direct for reaction
The cooling 30min of 10 DEG C of water, then catalyst is precipitated by centrifuge separation and vacuum drying drying recycling in reaction mass, catalyst returns
Yield is 96.4%, between 0.1~110 micron of catalyst particle size.
Comparative example 1-1
Under 1 equal conditions of embodiment, reaction mass is cooled to rapidly 20 DEG C after reaction, and additive phosphoric acid is added
Potassium, sodium phosphate 2g and aluminum oxide 0.25g, 20 DEG C of continuation insulated and stirred 30min are further continued for being cooled to 10 DEG C, stand
30min, reaction mass recycle by centrifuge separation and vacuum drying drying and catalyst are precipitated, catalyst recovery yield 99.9%,
Catalyst particle size is distributed as between 25~200 microns.
Comparative example 1-2
Under 1 equal conditions of embodiment, reaction mass is cooled to rapidly 20 DEG C after reaction, and additive phosphoric acid is added
0.5g and aluminum oxide 0.25g, 20 DEG C of continuation insulated and stirred 30min are further continued for being cooled to 10 DEG C, stand 30min, reactant
Catalyst, catalyst recovery yield 99.9%, catalyst particle size is precipitated by centrifuge separation and vacuum drying drying recycling in material
It is distributed as between 50~250 microns.
Embodiment 2
Chloropropene 309.0g and phosphato-molybdic heteropolyacid catalyst 15g is put into 500mL four-hole boiling flask, is warming up to reflux,
It is added dropwise 49.1% hydrogen peroxide 69.6g under stirring in 2h, the reaction was continued under reflux temperature 3h；Reaction was completed that material is direct for reaction
The cooling 30min of 10 DEG C of water, then catalyst is precipitated by centrifuge separation and vacuum drying drying recycling in reaction mass, catalyst returns
Yield is 97.9%, between 1~100 micron of catalyst particle size.
Comparative example 2
Under 2 equal conditions of embodiment, reaction mass is cooled to rapidly 0 DEG C after reaction, be added additive potassium sulfate,
Sodium sulphate 2g and silica 1 g, 0 DEG C of continuation insulated and stirred 15min stand 30min, and reaction mass is by centrifuge separation and very
The dry drying recycling of sky is precipitated catalyst, catalyst recovery yield 99.5%, catalyst particle size be distributed as 15~180 microns it
Between.
Embodiment 3
Chloropropene 309.0g and silicotungstic heteropolyacid catalyst 15g is put into 500mL four-hole boiling flask, is warming up to reflux,
It is added dropwise 49.1% hydrogen peroxide 69.6g under stirring in 2h, the reaction was continued under reflux temperature 3h；Reaction was completed that material is direct for reaction
The cooling 30min of 10 DEG C of water, then catalyst is precipitated by centrifuge separation and vacuum drying drying recycling in reaction mass, catalyst returns
Yield is 85.5%, between 0.1~90 micron of catalyst particle size.
Comparative example 3-1
Under 3 equal conditions of embodiment, reaction mass is cooled to rapidly 35 DEG C after reaction, and additive Boratex is added
0.05g and aluminum oxide 0.025g, 35 DEG C of continuation insulated and stirred 25min are further continued for being cooled to 10 DEG C, stand 30min, reaction
Catalyst, catalyst recovery yield 95.7%, catalyst granules is precipitated by centrifuge separation and vacuum drying drying recycling in material
Degree is distributed as between 1~160 micron.
Comparative example 3-2
Under 3 equal conditions of embodiment, reaction mass is cooled to rapidly 35 DEG C after reaction, and additive sodium metasilicate is added
0.10g and aluminum oxide 0.025g, 35 DEG C of continuation insulated and stirred 25min are further continued for being cooled to 10 DEG C, stand 30min, reaction
Catalyst, catalyst recovery yield 96.7%, catalyst granules is precipitated by centrifuge separation and vacuum drying drying recycling in material
Degree is distributed as between 20~260 microns.
Embodiment 4
Chloropropene 309.0g and ferrotungsten heteropolyacid catalyst 15g is put into 500mL four-hole boiling flask, is warming up to reflux,
It is added dropwise 49.1% hydrogen peroxide 69.6g under stirring in 2h, the reaction was continued under reflux temperature 3h；Reaction was completed that material is direct for reaction
The cooling 30min of 10 DEG C of water, then catalyst is precipitated by centrifuge separation and vacuum drying drying recycling in reaction mass, catalyst returns
Yield is 98.3%, between 0.5~130 micron of catalyst particle size.
Comparative example 4
Under 4 equal conditions of embodiment, reaction mass is cooled to rapidly 15 DEG C after reaction, and additive three is added and aoxidizes
Two aluminium 0.25g and silica 0.5g, 15 DEG C of continuation insulated and stirred 5min are further continued for being cooled to 10 DEG C, stand 30min, reaction
Catalyst, catalyst recovery yield 99.6%, catalyst granules is precipitated by centrifuge separation and vacuum drying drying recycling in material
Degree is distributed as between 10~170 microns.
Embodiment 5
Chloropropene 309.0g and iron molybdenum heteropolyacid catalyst 15g is put into 500mL four-hole boiling flask, is warming up to reflux,
It is added dropwise 49.1% hydrogen peroxide 69.6g under stirring in 2h, the reaction was continued under reflux temperature 3h；Reaction was completed that material is direct for reaction
The cooling 30min of 10 DEG C of water, then catalyst is precipitated by centrifuge separation and vacuum drying drying recycling in reaction mass, catalyst returns
Yield is 96.5%, between 0.5~140 micron of catalyst particle size.
Comparative example 5
Under 5 equal conditions of embodiment, reaction mass is cooled to rapidly 30 DEG C after reaction, be added additive sulfuric acid,
Ammonium sulfate 1.50g, 30 DEG C of continuation insulated and stirred 60min are further continued for being cooled to 10 DEG C, stand 30min, reaction mass is by centrifugation
Separation and vacuum drying drying recycling are precipitated catalyst, catalyst recovery yield 99.9%, and catalyst particle size is distributed as 30~
Between 200 microns.
Claims (10)
1. a kind of raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method, which is characterized in that after epoxidation reaction,
It is cooled to certain temperature rapidly, a certain amount of additive is then added into reaction solution, and after stirring a period of time, product warp
Catalyst is recycled in centrifugation.
2. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that described
Temperature be 0~35 DEG C.
3. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 2, which is characterized in that described
Temperature be 15~30 DEG C.
4. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that described
Additive be one or more of phosphate, silicate, sulfate, borate and metal oxide combination.
5. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that described
Phosphate be phosphoric acid, potassium phosphate, sodium phosphate, silicate is sodium metasilicate, and sulfate is sulfuric acid, potassium sulfate, sodium sulphate, sulfuric acid
Ammonium, borate are Boratex, and metal oxide is aluminum oxide, silica.
6. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that addition
Agent dosage is the 0.5~20wt% for putting into catalyst amount.
7. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 6, which is characterized in that addition
Agent dosage is the 5~15wt% for putting into catalyst amount.
8. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that described
Mixing time be 5~60min.
9. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 8, which is characterized in that described
Mixing time be 15~30min.
10. raising phosphorus tungsten/molybdenum heteropolyacid catalyst recovery yield method according to claim 1, which is characterized in that recycling
Catalyst particle size is distributed between 20~250 microns, wherein have 90wt% catalyst particle size be 90~150 microns between,
Catalyst recovery yield >=99.5%.
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