CN102746257B - Method for preparing epichlorohydrin by chloropropene epoxidation - Google Patents
Method for preparing epichlorohydrin by chloropropene epoxidation Download PDFInfo
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- CN102746257B CN102746257B CN201210225716.2A CN201210225716A CN102746257B CN 102746257 B CN102746257 B CN 102746257B CN 201210225716 A CN201210225716 A CN 201210225716A CN 102746257 B CN102746257 B CN 102746257B
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- hydrogen peroxide
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Abstract
The invention relates to a method for preparing epichlorohydrin by chloropropene epoxidation. The method comprises steps of: directly adding tungstic acid, phosphoric acid, cetyl trimethyl ammonium bromide, hydrogen peroxide and chloropropene in a container, so as to synthesize a phosphotungstic heteropolyacid quaternary ammonium salt catalyst and epichlorohydrin without separation in a reaction system; after the reaction, carrying out oil-water separation to retain the catalyst in the aqueous phase; and then directly adding hydrogen peroxide and catalyst for epoxidation again. The epichlorohydrin synthesis method without separation provided by the present invention does not need separate preparation of the catalyst, saves operation steps and a large quantity of solvent, has an epichlorohydrin yield reaching more than 86%, and reduces production cost.
Description
Technical field
The present invention relates to a kind of method of preparing epichlorohydrin by chloropropene epoxidation.
Technical background
Epoxy chloropropane (claim again Epicholorohydrin, English name epichlorohydrin, is called for short ECH) is a kind of important Organic Chemicals and intermediate.Industrial production mainly contains propylene high-temperature chlorination process and acetic acid allyl acetate-allyl alcohol method at present.Two kinds of methods all exist to be polluted and the serious defect of equipment corrosion, and technical process is long.
With eco-friendly H
2o
2it for oxygen source, is one of study hotspot of propenyl chloride catalysis epoxidation in recent years.The method that at present document is announced have the titanium molecular sieve catalysis of use method (as: catalysis journal, 2006,27(8): 656-658) and phospho heteropoly tungstate catalysis method (as: Journal of Molecular Catalysis, 2010,24(5): 387-391).HTS system preparation cost is high, and reaction process needs polar solvent.Phosphorus heteropoly tungstic acid salt catalyst feature be under homogeneous phase condition with H
2o
2initial ring oxidizing reaction, after reaction finishes, H
2o
2be exhausted, catalyzer is separated out from reaction system, can reclaim and reuse.Document (as: Organic Process Research & Development, 2006,10:876-880) announced the preparation method of quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer.But the preparation of catalyzer need be carried out separately, and step is more numerous and diverse, and in preparation process, need to consume extra H
2o
2with a large amount of organic solvents.
Summary of the invention
For existing catalyzer preparation need be independent of the step of epoxidation reaction and preparation process step more numerous and diverse and in preparation process, need to consume extra H
2o
2with the problem of a large amount of solvents, a kind of method of preparing epichlorohydrin by chloropropene epoxidation is provided, adopt the method without independent Kaolinite Preparation of Catalyst, step is few, saves hydrogen peroxide and a large amount of solvent.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: wolframic acid, phosphoric acid, cetyl trimethylammonium bromide, Sodium phosphate dibasic, hydrogen peroxide and propenyl chloride are directly added in flask, in reaction system, without separation, synthesize quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer and epoxy chloropropane; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, more directly adds the hydrogen peroxide of proportional quantity and propenyl chloride to carry out epoxidation again.
Wherein, concrete steps are: in container, add phosphotungstic acid quaternary formula weight Q
3[PW
4o
16meter] SODIUM PHOSPHATE, MONOBASIC of wolframic acid, cetyl trimethylammonium bromide (Q in formula weight) and total reactant quality 0.05% of proportioning, and epoxidation proportioning (mole) propenyl chloride (propenyl chloride: hydrogen peroxide=4:1), under room temperature (≤25 ℃) and whipped state, add epoxidation proportional quantity (mole) half superoxol, react 20 minutes; Then mass concentration 85% phosphoric acid that adds proportional quantity, continue to stir 15min-20min, then adds residue superoxol, and is slowly warming up to set(ting)value and carries out epoxidation reaction; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, directly adds hydrogen peroxide and the propenyl chloride of proportional quantity, then repeats epoxidation.
Wherein, the superoxol mass concentration of half first adding is 25%, and the superoxol mass concentration of remainder is 50%.
Wherein, a catalyzer generation section temperature is controlled at below room temperature (≤25 ℃); Epoxidation reaction temperature first rises to 40 ℃ from room temperature, is more slowly increased to 55-65 ℃.
Catalyzer to reuse process as follows: after epoxidation reaction finishes, product epoxy chloropropane and unreacted propenyl chloride are in upper oil phase, and catalyzer is at lower floor's water; After the separation of oil-water, directly in water, add the propenyl chloride of proportional quantity and hydrogen peroxide to carry out again epoxidation reaction.
Advantage of the present invention is:
1, directly in container, add wolframic acid, phosphoric acid, cetyl trimethylammonium bromide and hydrogen peroxide and propenyl chloride, in reaction system, without separation, synthesize quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer and epoxy chloropropane, without independent Kaolinite Preparation of Catalyst, save operation steps and extra hydrogen peroxide and a large amount of solvent, simplified operation steps; Experimental result confirmation, the productive rate of epoxy chloropropane reaches more than 86%, and this method is used in industrial production and will be greatly reduced production costs.
2, with Introduction of Literatures (as: Organic Process Research & Development, 2006,10:876-880) difference of independent Kaolinite Preparation of Catalyst is, solvent extraction and oil-aqueous phase separation are not passed through in generation without separating catalyst, in solution, still remain with the bromide anion that quaternary ammonium salt brings, epoxidation be there is no to undesirable action, but can change pH value of solution, in container, add the hydrolysis that Sodium phosphate dibasic effectively stops product.
Accompanying drawing explanation
Fig. 1 is the catalyzer infrared spectrogram that the present invention is prepared without separation.
Fig. 2 is the affect figure of temperature on epoxy chloropropane productive rate.
Fig. 3 is that epoxy chloropropane productive rate is schemed over time.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical solution of the present invention, these embodiment can not be interpreted as it is the restriction to technical scheme.
Embodiment 1: in container, add phosphotungstic acid quaternary formula weight Q
3[PW
4o
16meter] SODIUM PHOSPHATE, MONOBASIC of wolframic acid, cetyl trimethylammonium bromide (Q in formula weight) and total reactant quality 0.05% of proportioning, and epoxidation proportioning (mole) propenyl chloride (propenyl chloride: hydrogen peroxide=3:1), under room temperature (≤25 ℃) and whipped state, add epoxidation proportional quantity (mole) superoxol that half mass concentration is 25%, react 20 minutes; Then mass concentration 85% phosphoric acid that adds proportional quantity, continue to stir 15min-20min, then to add remaining mass concentration be 50% superoxol, first from room temperature, rises to 40 ℃, is more slowly increased to 55 ℃ and carries out epoxidation reaction 5 hours; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, directly adds hydrogen peroxide and the propenyl chloride of proportional quantity, then repeats epoxidation.
Embodiment 2: in container, add phosphotungstic acid quaternary formula weight Q
3[PW
4o
16meter] SODIUM PHOSPHATE, MONOBASIC of wolframic acid, cetyl trimethylammonium bromide (Q in formula weight) and total reactant quality 0.05% of proportioning, and epoxidation proportioning (mole) propenyl chloride (propenyl chloride: hydrogen peroxide=4:1), under room temperature (≤25 ℃) and whipped state, add epoxidation proportional quantity (mole) superoxol that half mass concentration is 25%, react 20 minutes; Then mass concentration 85% phosphoric acid that adds proportional quantity, continue to stir 15min-20min, then to add remaining mass concentration be 50% superoxol, first from room temperature, rises to 40 ℃, is more slowly increased to 60 ℃ and carries out epoxidation reaction 4; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, directly adds hydrogen peroxide and the propenyl chloride of proportional quantity, then repeats epoxidation.
Embodiment 3: in container, add phosphotungstic acid quaternary formula weight Q
3[PW
4o
16meter] SODIUM PHOSPHATE, MONOBASIC of wolframic acid, cetyl trimethylammonium bromide (Q in formula weight) and total reactant quality 0.05% of proportioning, and epoxidation proportioning (mole) propenyl chloride (propenyl chloride: hydrogen peroxide=5:1), under room temperature (≤25 ℃) and whipped state, add epoxidation proportional quantity (mole) superoxol that half mass concentration is 25%, react 20 minutes; Then mass concentration 85% phosphoric acid that adds proportional quantity, continue to stir 15min-20min, then to add remaining mass concentration be 50% superoxol, first from room temperature, rises to 40 ℃, is more slowly increased to 65 ℃ and carries out epoxidation reaction 4; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, directly adds hydrogen peroxide and the propenyl chloride of proportional quantity, then repeats epoxidation.
The solid particulate infrared spectrogram without separation after separating reaction that embodiments of the invention obtain is as Fig. 1, (the Organic Process Research & Development of each charateristic avsorption band and bibliographical information in figure, 2006,10:876-880 and catalysis journal, 2005,26(11): the catalyzer of independent preparation 1005-1010) is basically identical, show that the material generating is quaternary ammonium salt phosphor-tungstic heteropoly acid really.
Under identical epoxidation conditions (60 ℃, 4 hours), by the epoxy chloropropane productive rate obtaining without separating reaction (for the first time) of the present invention and the catalyzer (reference literature that adds independent preparation
[13]preparation), the former productive rate is 86.32% to the productivity ratio of the lower reaction of effect, and the latter is 87.47%, shows that two kinds of methods prepare epoxy chloropropane, and productive rate is very nearly the same.
From embodiment, temperature is on the impact of epoxidation reaction products collection efficiency as Fig. 2, and the reaction times is 4 hours, and when temperature is 60 ℃, products collection efficiency is the highest, is 86.32%; When temperature is respectively 55 ℃ and 65 ℃, productive rate is respectively 78.35% and 83.17%.
From embodiment, the time on the impact of epoxidation reaction products collection efficiency as Fig. 3, the highest at 5 hours epoxy chloropropane productive rates, reach 85.43%; And react 4 hours, system just approaches balance, and productive rate reaches 84.52%.
From embodiment, when propenyl chloride and hydrogen peroxide mol ratio are respectively 3:1,4:1,5:1, the productive rate that obtains epoxy chloropropane should be 79.35%, 85.63%, 86.22% mutually.
Of the present invention without separating ring oxidizing reaction for the first time synthetic productive rate be 85.95%, catalyzer is reused once, productive rate is 84 .87%, with synthetic yield comparison for the first time, very approaching.
Claims (3)
1. the method for preparing epichlorohydrin by chloropropene epoxidation, the method is that wolframic acid, phosphoric acid, cetyl trimethylammonium bromide, Sodium phosphate dibasic, hydrogen peroxide and propenyl chloride are directly added in flask, in reaction system, without separation, synthesizes quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer and epoxy chloropropane; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, more directly adds the hydrogen peroxide of proportional quantity and propenyl chloride to carry out epoxidation again; It is characterized in that: in container, add phosphotungstic acid quaternary formula weight Q
3[PW
4o
16meter] SODIUM PHOSPHATE, MONOBASIC of Q and total reactant quality 0.05% in the wolframic acid, cetyl trimethylammonium bromide formula weight of proportioning, and the propenyl chloride of epoxidation mole proportioning, propenyl chloride: hydrogen peroxide=5-3:1, under room temperature and whipped state, add half superoxol of epoxidation mole proportional quantity, react 20 minutes; Then mass concentration 85% phosphoric acid that adds proportional quantity, continue to stir 15min-20min, then adds residue superoxol, and is slowly warming up to 55-65 ℃ of set(ting)values and carries out epoxidation reaction 4-5 hour; After reaction finishes, by oil-water two, be separated, catalyzer is retained in water, directly adds hydrogen peroxide and the propenyl chloride of proportional quantity, then repeats epoxidation.
2. the method for preparing epichlorohydrin by chloropropene epoxidation according to claim 1, is characterized in that: the superoxol mass concentration of half first adding is 25%, and the superoxol mass concentration of remainder is 50%.
3. the method for preparing epichlorohydrin by chloropropene epoxidation according to claim 1, is characterized in that: catalyzer generates section temperature and is controlled at below room temperature; Epoxidation reaction temperature first rises to 40 ℃ from room temperature, is more slowly increased to 55-65 ℃.
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