CN103664832A - Method for producing epoxy propane through direct epoxidation of propylene - Google Patents
Method for producing epoxy propane through direct epoxidation of propylene Download PDFInfo
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- CN103664832A CN103664832A CN201210324480.8A CN201210324480A CN103664832A CN 103664832 A CN103664832 A CN 103664832A CN 201210324480 A CN201210324480 A CN 201210324480A CN 103664832 A CN103664832 A CN 103664832A
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- propylene
- propylene oxide
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 35
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 26
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 238000005119 centrifugation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002223 garnet Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- JHZRQBKLEHQTKF-UHFFFAOYSA-N 2-methyloxirane;prop-1-ene Chemical compound CC=C.CC1CO1 JHZRQBKLEHQTKF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- B01J35/50—
-
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention relates to a method for producing epoxy propane through direct epoxidation of propylene, which is mainly used for solving the problems of excess reaction temperature of direct epoxidation of a propylene gas phase and low selectivity of epoxy propane in the prior art. In the method provided by the invention, propylene and air are adopted as raw materials; the raw materials are in contact with a catalyst to generate epoxy propane under the conditions that the molar ratio of propylene to oxygen is (1/5)-(1/10), the reaction temperature is 150-250 DEG C, the reaction pressure is 0.8-2MPa and the air speed is 1,000-5,000/h, wherein the catalyst is nano hollow-structure iron molybdate with a chemical general formula Fe2(MoO4)3. By adopting the technical scheme, the problems are better solved, and the method can be applied to the industrial production of producing epoxy propane through direct epoxidation of propylene and air.
Description
Technical field
The present invention relates to a kind of propylone direct opoxidation and produce the method for propylene oxide.
Background technology
Propylene oxide is very important basic organic chemical industry raw material, is the second largest derivative of propylene.The purposes of propylene oxide maximum is for the production of polyether glycol, accounts for 60% of its total quantity consumed, is further processed as the important intermediate-urethane of synthetic plastics and fiber.In recent years, due to the expansion of Downstream Market, propylene oxide demand significantly increases year by year.
The existing production technique of propylene oxide is mainly chlorohydrination and conjugated oxidation (claiming again peroxidation method or indirect oxidation method).The advantage of chlorohydrination is that flow process is short, technical maturity, turndown ratio is large, little to raw material propylene purity requirement, facility investment is few.But 40 ~ 50 tons of 1 ton of propylene oxide by-products of every production are containing 2 ~ 3 % by weight CaCl in chlorohydrination technological process
2with the waste water of organochlorine, environmental problem becomes increasingly conspicuous.Conjugated oxidation refers to organo-peroxides such as utilizing tertbutyl peroxide or ethylbenzene hydroperoxide, and co-oxidation propylene generates propylene oxide.The method produces a large amount of joint product vinylbenzene or the trimethyl carbinol, and 1 ton of propylene oxide of every production approximately has 2.5 tons of trimethyl carbinols or 1.8 tons of vinylbenzene substantially, has restricted its application.Therefore, direct oxidation of propylene method has caused people's extensive concern, wherein with the direct selective oxidation propylene of the molecular oxygen atomic economy reaction of Worth Expecting especially.
Document (
chem. Eng. News, 2001,79,19.) and summed up catalytic material and the technological process of utilizing oxygen gas phase direct oxidation production of propylene propylene oxide, catalytic material comprises the systems such as Ag base, Cu base, but exists temperature of reaction high, the problems such as propylene oxide selectivity.How to reduce temperature of reaction, avoid the conversion under propylene oxide high temperature, improve the difficulties that its selectivity is this reaction.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists Direct Vapor-Phase Epoxidation of Propylene temperature of reaction too high, and propylene oxide is selected low problem, provides a kind of new propylone direct opoxidation to produce the method for propylene oxide.It is low that the method has temperature of reaction, the feature that propylene oxide selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of propylone direct opoxidation is produced the method for propylene oxide, take propylene and air as raw material, at propylene and oxygen mol ratio, be 1/5 ~ 1/10, temperature of reaction is 150 ~ 250 ℃, reaction pressure is 0.8 ~ 2MPa, and air speed is 1000 ~ 5000 hours
-1condition under, raw material contacts with catalyzer and generates propylene oxide; Described catalyzer is that chemical general formula is Fe
2(MoO
4)
3nano hollow structure iron molybdate.
In technique scheme, the thickness preferable range of described nano hollow structure iron molybdate is 10 ~ 50 nanometers.Described nano hollow structure preferred version is nano tubular structure, and described nano tubular structure length is 1 ~ 2 millimeter, and diameter is 100 ~ 200 nanometers.Temperature of reaction preferable range is 160 ~ 230 ℃, and reaction pressure preferable range is 1.0 ~ 1.5MPa, and reaction velocity preferable range is 2000 ~ 3000 hours
-1.
In technique scheme, the preparation method of described nano hollow structure iron molybdate, comprises the following steps: a) molybdenum source is dissolved in solvent I, forms mixture I; By mixture I, under 150 ~ 200 ℃ of conditions, hydrothermal crystallizing 1 ~ 48 hour, obtains intermediate A; Wherein, described molybdenum source is selected from molybdenum oxide or Ammonium Heptamolybdate; Solvent I is selected from 5 ~ 15mol/L hydrogen peroxide, hydrochloric acid, nitric acid or aqueous sulfuric acid; The weight ratio of molybdenum source and solvent I is 1/4 ~ 1/50;
B) intermediate A is added in solvent II, form mixture II; By containing the inorganic salt of Fe ion 30 ~ 80 ℃ join mixture II among, ageing 0.5 ~ 24 hour, obtains intermediate B after washing; Wherein, the weight ratio of intermediate A and solvent II is 1/10 ~ 1/50; Solvent II is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1/1 ~ 30/1, and alcohol is selected from ethanol, propyl alcohol or propylene glycol; The weight ratio of mixture II and inorganic salt is 1/5 ~ 1/40;
C) intermediate B heats 1 ~ 48 hour under 300 ~ 450 ℃ of conditions, obtains described nano hollow structure iron molybdate Fe
2(MoO
4)
3.
In technique scheme, step a), hydrothermal crystallizing temperature preferable range is 155 ~ 190 ℃, hydrothermal crystallizing time preferable range is 10 ~ 30 hours; Molybdenum source preferred version is for being selected from molybdenum oxide, and solvent I preferred version is for being selected from hydrogen peroxide or hydrochloric acid soln.Step b), in solvent II, the weight ratio preferable range of water and alcohol is 10/1 ~ 25/1.Step c), temperature preferable range is 320 ~ 400 ℃, time preferable range is 5 ~ 20 hours.
In technique scheme, described intermediate A is the α-MoO of nanometer monocrystalline four directions rod
3, belong to rhombic system, { the 100} crystal face that outside surface is rhombic system.Described intermediate B is MoO
3/ FeO
xone-dimensional nucleocapsid structure.
The preparation method in the inventive method with nano hollow structure iron molybdate, first, by the method for hydrothermal recrystallization method, prepares monocrystalline molybdenum oxide nanometer four directions rod; Then, by controlled hydrolysis sedimentation chemistry method, on the outside surface of monocrystalline molybdenum oxide nanometer four directions club shaped structure, deposit Fe species, form nano core-shell structure; Finally, by the thermal treatment under still air of nano core-shell structure, prepare nano hollow structure iron molybdate.The inventive method utilizes one-dimensional nucleocapsid structure for precursor, selects two kinds of metal oxide materials that rate of diffusion is different, under nanoscale, controls thermodiffusion, has synthesized the hollow structure under nanoscale.
Nano structural material has that specific surface area is large, interface atom is many, interface zone atomic diffusivity is high, and has preferentially high preferred orientation and very high chemically reactive, thereby, in the world using its as the 4th generation catalyzer carry out research and development.Nano-particle catalyst has high activity and good selectivity to cause catalysis worker's attention.Compare with nano particle, nano tubular structure specific surface area increases, and the one-dimensional channels providing can be as nano-reactor in catalyzed reaction, the collision of modulation reactant molecule, intermediate state product and tube wall, thus affect reaction kinetics and products distribution.The present invention utilizes monocrystalline molybdenum oxide nanometer four directions club shaped structure, and then controlled hydrolysis formation of deposits nanostructure nucleocapsid precursor prepares the catalytic material of nano hollow structure molybdate.
The inventive method is to take nano hollow structure iron molybdate as catalyzer, and in fixed-bed reactor, propylene and the reaction of air gas phase Direct Epoxidation generate propylene oxide.Compare with common block iron molybdate catalyzer, nano hollow structure iron molybdate has the performance of catalytic oxidation propylene generation propylene oxide under low temperature (temperature can reduce by 100 ℃), in catalyzer unit surface, the transformation efficiency of propylene molecules improves more than 18 times simultaneously, has obtained good technical result.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction figure of intermediate A, B and finished product iron molybdate synthetic in the present invention [embodiment 1 ~ 2].
Fig. 2 is molybdenum oxide nanometer four directions rod synthetic in the present invention [embodiment 1 ~ 4], i.e. the projection Electronic Speculum figure of intermediate A.
Fig. 3 is synthetic MoO in the present invention [embodiment 1]
3/ FeO
xnucleocapsid structure, i.e. the projection Electronic Speculum figure of intermediate B.
Fig. 4 is synthetic MoO in the present invention [embodiment 2] and [embodiment 4]
3/ FeO
xnucleocapsid structure, i.e. the projection Electronic Speculum figure of intermediate B.
Fig. 5 is the projection Electronic Speculum figure of finished product iron molybdate synthetic in the present invention [embodiment 2] and [embodiment 4].
Fig. 6 is the projection Electronic Speculum figure of single nano hollow structure iron molybdate synthetic in the present invention [embodiment 2] and [embodiment 4].
In Fig. 1, a is monocrystalline molybdenum oxide nanometer rod, i.e. intermediate A.B is MoO
3/ FeO
xnucleocapsid structure, i.e. intermediate B, this explanation shell is amorphous.The nano hollow structure iron molybdate that c is 20nm for [embodiment 1] thickness, the nano hollow structure iron molybdate that d is 40nm for [embodiment 2] thickness, shows and has finally formed oblique system iron molybdate.
Fig. 2, shows molybdenum oxide nanometer four directions rod synthetic in [embodiment 1 ~ 4], and length is 1 ~ 10 μ m, and wide is 100 ~ 200nm, and height is 20 ~ 40nm.
In Fig. 3, show synthetic MoO in [embodiment 1]
3/ FeO
xnucleocapsid structure, i.e. intermediate B shell homogeneous very, thickness is 20nm.
In Fig. 4, show synthetic MoO in [embodiment 2] and [embodiment 4]
3/ FeO
xnucleocapsid structure, the shell thickness of intermediate B is 40nm.
In Fig. 5, show that in [embodiment 2] and [embodiment 4], synthetic finished product iron molybdate length is 1 ~ 10 μ m, wide is 100 ~ 200nm, and this is consistent with precursor molybdenum oxide nanometer four directions rod.
In Fig. 6, show the projection Electronic Speculum figure of single nano hollow structure iron molybdate synthetic in the present invention [embodiment 2] and [embodiment 4], wherein, single nano hollow structure material is carried out to electron spectroscopy analysis everywhere, the Mo/Fe atomic ratio that shows three places is respectively 1.6,2.1,1.7.This illustrates the Mo/Fe reduction from inside to outside of single nano hollow structure, meets the ultimate principle that forms concentration gradient in thermodiffusion.
Below by embodiment, the present invention is further elaborated.
Embodiment
In the present invention, disclosed nano hollow structure iron molybdate preparation method is divided into three parts: first, utilize the chemical process of hydrothermal recrystallization method, prepare molybdenum oxide nanometer four directions club shaped structure; Secondly, on the bar-shaped outside surface in molybdenum oxide nanometer four directions of preparing in previous step, deposit FeO
xshell, the MoO of formation different thickness
3/ FeO
xnucleocapsid structure, the chemical process of using controlled hydrolysis to deposit; Finally, in still air atmosphere, nucleocapsid structure prepared by previous step is heat-treated, and forms nano hollow structure iron molybdate material.
[embodiment 1]
Get 30% H that commodity molybdenum oxide powder 10mmol joins 70ml
2o
2in solution, stirring at room 1 day, then transfers in hydrothermal reaction kettle, at 180 ℃ of baking ovens, keeps 24 hours.Then take out, centrifugation, adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
The molybdenum oxide nanometer four directions club-shaped material of above-mentioned preparation is joined in water and ethanol mixed system, and the weight ratio of water and ethanol is to stir half an hour at 5/1,70 ℃, then by FeCl
3alcohol solution, joins above-mentioned suspension liquid system, wherein, and FeCl
3with MoO
3mol ratio be 2:3; Then, ageing 24 hours, obtains maroon suspension, and centrifugation adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains garnet powder, is MoO
3/ FeO
xnucleocapsid structure.
By the thickness of above-mentioned preparation, be 20nm MoO
3/ FeO
xnucleocapsid structure is transferred to baking oven, in still air atmosphere, with the temperature rise rate to 400 of 10K/min ℃, keeps 10 hours, and naturally cooling, obtains the powder of grey; Being thickness is the nano hollow structure iron molybdate novel material of 20nm.
[embodiment 2]
The hydrochloric acid of 2 M is dropwise joined in the Ammoniun Heptamolybdate Solution of 10mmol, stirring at room 2 days, then gets 70ml solution and transfers in hydrothermal reaction kettle, at 180 ℃ of baking ovens, keeps 24 hours.Then take out, centrifugation, adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
The molybdenum oxide nanometer four directions club-shaped material of above-mentioned preparation is joined in water and ethanol mixed system, and the weight ratio of water and ethanol is at 10/1,100 ℃, to stir 1 hour, then by FeCl
3alcohol solution, joins above-mentioned suspension liquid system, FeCl
3with MoO
3mol ratio be 1:1; Then, ageing 24 hours, obtains maroon suspension, and centrifugation adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains garnet powder, is MoO
3/ FeO
xnucleocapsid structure.
By the thickness of above-mentioned preparation, be 40nm MoO
3/ FeO
xnucleocapsid structure is transferred to baking oven, in still air atmosphere, with temperature rise rate to 350 ~ 450 of 1K/min ~ 40K/min ℃, keeps 5 ~ 48 hours, and naturally cooling, obtains the powder of grey.Wherein, the temperature rise rate of preferred 10K/min, temperature of reaction is 420 ℃, and the reaction times is 10 hours, and finally preparing thickness is the nano hollow structure iron molybdate novel material of 40nm.
[embodiment 3]
Get 30% H that commodity molybdenum oxide powder 10mmol joins 70ml
2o
2in solution, stirring at room 1 day, then transfers in hydrothermal reaction kettle, at 180 ℃ of baking ovens, keeps 24 hours.Then take out, centrifugation, adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
The molybdenum oxide nanometer four directions club-shaped material of above-mentioned preparation is joined in water and propyl alcohol mixed system, and the weight ratio of water and propyl alcohol is to stir half an hour at 5/1,70 ℃, then by FeCl
3alcohol solution, joins above-mentioned suspension liquid system, wherein, and FeCl
3with MoO
3mol ratio be 3:4; Then, ageing 24 hours, obtains maroon suspension, and centrifugation adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains garnet powder, is MoO
3/ FeO
xnucleocapsid structure.
By the thickness of above-mentioned preparation, be 30nm MoO
3/ FeO
xnucleocapsid structure is transferred to baking oven, in still air atmosphere, with the temperature rise rate to 400 of 10K/min ℃, keeps 10 hours, and naturally cooling, obtains the powder of grey; Being thickness is the nano hollow structure iron molybdate novel material of 30nm.
[embodiment 4]
Get 30% H that commodity molybdenum oxide powder 10mmol joins 70ml
2o
2in solution, stirring at room 1 day, then transfers in hydrothermal reaction kettle, at 180 ℃ of baking ovens, keeps 24 hours.Then take out, centrifugation, adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
The molybdenum oxide nanometer four directions club-shaped material of above-mentioned preparation is joined in water and ethanol mixed system, and the weight ratio of water and propylene glycol is to stir half an hour at 10/1,70 ℃, then by FeCl
3alcohol solution, joins above-mentioned suspension liquid system, wherein, and FeCl
3with MoO
3mol ratio be 1:1; Then, ageing 24 hours, obtains maroon suspension, and centrifugation adopts deionized water wash three times, and then washing with alcohol is three times, and oven drying at low temperature obtains garnet powder, is MoO
3/ FeO
xnucleocapsid structure.
By the thickness of above-mentioned preparation, be 40nm MoO
3/ FeO
xnucleocapsid structure is transferred to baking oven, in still air atmosphere, with the temperature rise rate to 420 of 10K/min ℃, keeps 5 hours, and naturally cooling, obtains the powder of grey; Being thickness is the nano hollow structure iron molybdate novel material of 40nm.
[embodiment 5]
Catalyzed reaction characterizes: get the nano hollow structure iron molybdate catalyzer of 0.2 gram [embodiment 1 ~ 3] preparing and join in heterogeneous fixed bed micro-reaction device, pass into propylene and air, heat and react.Wherein, temperature of reaction is 150 ~ 250 ℃, and reaction pressure is 0.8 ~ 2MPa, the results are shown in Table 1.
?
[comparative example 1]
By business product molybdenum oxide and ferric oxide solid phase mixing, wherein, the weight ratio of molybdenum oxide and ferric oxide is 2:1, solid-phase ball milling 5 hours, then, in still air atmosphere, with the temperature rise rate to 500 of 10K/min ℃, keep 5 hours, naturally cooling, obtains the powder of grey; Be Traditional bulk iron molybdate material, be designated as FeMo-c.According to its catalytic activity of method evaluation of [embodiment 5].The results are shown in Table 1.
Table 1
Claims (9)
1. propylone direct opoxidation is produced a method for propylene oxide, take propylene and air as raw material, at propylene and oxygen mol ratio, is 1/5 ~ 1/10, and temperature of reaction is 150 ~ 250 ℃, and reaction pressure is 0.8 ~ 2MPa, and air speed is 1000 ~ 5000 hours
-1condition under, raw material contacts with catalyzer and generates propylene oxide; Described catalyzer is that chemical general formula is Fe
2(MoO
4)
3nano hollow structure iron molybdate.
2. propylone direct opoxidation according to claim 1 is produced the method for propylene oxide, and the thickness that it is characterized in that described nano hollow structure iron molybdate is 10 ~ 50 nanometers.
3. propylone direct opoxidation according to claim 1 is produced the method for propylene oxide, it is characterized in that described nano hollow structure is nano tubular structure.
4. propylone direct opoxidation according to claim 3 is produced the method for propylene oxide, it is characterized in that described nano tubular structure length is 1 ~ 2 millimeter, and diameter is 100 ~ 200 nanometers.
5. propylone direct opoxidation according to claim 1 is produced the method for propylene oxide, it is characterized in that the preparation method of described nano hollow structure iron molybdate, specifically comprises the following steps:
A) molybdenum source is dissolved in solvent I, forms mixture I; By mixture I, under 150 ~ 200 ℃ of conditions, hydrothermal crystallizing 1 ~ 48 hour, obtains intermediate A; Wherein, described molybdenum source is selected from molybdenum oxide or Ammonium Heptamolybdate; Solvent I is selected from 5 ~ 15mol/L hydrogen peroxide, hydrochloric acid, nitric acid or aqueous sulfuric acid; The weight ratio of molybdenum source and solvent I is 1/4 ~ 1/50;
B) intermediate A is added in solvent II, form mixture II; By containing the inorganic salt of Fe ion 30 ~ 80 ℃ join mixture II among, ageing 0.5 ~ 24 hour, obtains intermediate B after washing; Wherein, the weight ratio of intermediate A and solvent II is 1/10 ~ 1/50; Solvent II is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1/1 ~ 30/1, and alcohol is selected from ethanol, propyl alcohol or propylene glycol; The weight ratio of mixture II and inorganic salt is 1/5 ~ 1/40;
C) intermediate B heats 1 ~ 48 hour under 300 ~ 450 ℃ of conditions, obtains described nano hollow structure iron molybdate Fe
2(MoO
4)
3.
6. propylone direct opoxidation according to claim 5 is produced the method for propylene oxide, it is characterized in that step a), and hydrothermal crystallizing temperature is 155 ~ 190 ℃, and the hydrothermal crystallizing time is 10 ~ 30 hours; Molybdenum source is selected from molybdenum oxide, and solvent I is selected from hydrogen peroxide or hydrochloric acid soln; Step b), in solvent II, the weight ratio of water and alcohol is 10/1 ~ 25/1; Step c), temperature is 320 ~ 400 ℃, the time is 5 ~ 20 hours.
7. propylone direct opoxidation according to claim 5 is produced the method for propylene oxide, it is characterized in that described intermediate A is the α-MoO of nanometer monocrystalline four directions rod
3, belong to rhombic system, { the 100} crystal face that outside surface is rhombic system.
8. propylone direct opoxidation according to claim 5 is produced the method for propylene oxide, it is characterized in that described intermediate B is MoO
3/ FeO
xlower one-dimensional nucleocapsid structure.
9. propylone direct opoxidation according to claim 1 is produced the method for propylene oxide, it is characterized in that temperature of reaction is 160 ~ 230 ℃, and reaction pressure is 1.0 ~ 1.5MPa, and the air speed of reaction is 2000 ~ 3000 hours
-1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106290187A (en) * | 2016-07-31 | 2017-01-04 | 国家***第海洋研究所 | A kind of Fe2(MoO4)3analogue enztme material |
| CN108440486A (en) * | 2018-03-27 | 2018-08-24 | 中国石油化工股份有限公司 | A kind of method of synthesizing acrylic ester |
| CN112916019A (en) * | 2021-01-26 | 2021-06-08 | 西南化工研究设计院有限公司 | Ferromolybdenum catalyst with core-shell structure, preparation and application |
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| CN106290187A (en) * | 2016-07-31 | 2017-01-04 | 国家***第海洋研究所 | A kind of Fe2(MoO4)3analogue enztme material |
| CN108440486A (en) * | 2018-03-27 | 2018-08-24 | 中国石油化工股份有限公司 | A kind of method of synthesizing acrylic ester |
| CN112916019A (en) * | 2021-01-26 | 2021-06-08 | 西南化工研究设计院有限公司 | Ferromolybdenum catalyst with core-shell structure, preparation and application |
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