CN100516056C - Method of preparing and separating epichlorohydrin by chloropropene epoxidation - Google Patents
Method of preparing and separating epichlorohydrin by chloropropene epoxidation Download PDFInfo
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- CN100516056C CN100516056C CNB2006101369235A CN200610136923A CN100516056C CN 100516056 C CN100516056 C CN 100516056C CN B2006101369235 A CNB2006101369235 A CN B2006101369235A CN 200610136923 A CN200610136923 A CN 200610136923A CN 100516056 C CN100516056 C CN 100516056C
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- epoxy chloropropane
- chloropropene
- propenyl chloride
- epichlorohydrin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses an epoxidizing method of epoxy chloropropane through chloropropene, which comprises the following steps: adopting excessive chloropropene to produce epoxy chloropropane directly under phosphotungstic acid quaternaries as catalyst and alkyl phenol polyoxyethylene ester as adjuvant catalyst and hydrogen peroxide solution as oxidant to reflux; cooling reactant; recycling solid-phased catalyst; distilling oil phase of reacting liquid to recycle residual chloropropene; decompressing; distilling; obtaining the purified product.
Description
Technical field
The present invention relates to a kind of processing method with propenyl chloride preparation and separation purification epoxy chloropropane.
Background technology
Present epoxy chloropropane production is based on chlorohydrination, but because this process spent water quantity discharged is big, environment is caused great pollution, process supplies consumption height, and the energy consumption height is so that production cost of products is too high.Therefore, each state all can replace the environment-friendly type technique of traditional technology in research.
The technology of exploring at present is various, but the most noticeablely has only HTS method and phospho-wolframic acid heteropolyacid method.In the HTS France, all make excessive quantity research abroad, but do not see industrialized report so far.
Nineteen eighty-three, Venturello reports Na
2WO
4/ PO
4/ R
4N
+Cl (quaternary ammonium salt muriate)/H
2O
2The phase-transfer catalysis epoxidation systems.This catalyst system can be water oil two-phase reaction system, with 8%H
2O
2The aqueous solution is oxygen source, 1, and the 2-ethylene dichloride is a solvent, the relative H of alkene in the reaction
2O
2Excessive.Because epoxide is present in the oil phase, has reduced the chance that contacts with water, and, can suppress the hydrolysis of epoxide effectively by regulating the pH value of water.
Ishii had reported HyPW in 1988
12O
40/ R
4N
+Cl/H
2O
2[R
4N
+]
3[PW
12O
40]
3-The epoxy catalyst system, after studies have shown that the catalyzer [R in the Ishii system
4N
+]
3[PW
12O
40]
3-In epoxidation reaction, be converted into [R
4N
+]
3{ PO
4[WO (O
2)
2]
4}
3-Ishii obtain with the Venturello system in active specy be identical.
1999, Dalian Inst of Chemicophysics, Chinese Academy of Sciences applied for the patent (CN 1155587C) of " preparing epoxy chloropropane by catalytic epoxidation of chloropropene by molecular oxygen ", was to be oxygen source with the molecular oxygen, was the operational path of catalyzer with the transistion metal compound.This patent activate molecular oxygen in organic solvent makes the propenyl chloride selective oxidation produce epoxy chloropropane.Be reflected under 30 ℃～80 ℃ and the 1atm～4atm and carry out, with quinones, azophenlyene or azo-compound is reductive agent, under the effect of filtering metal compound (catalyzer) and organic solvent, activated the Sauerstoffatom and the reductive agent effect of molecular oxygen, it is epoxy chloropropane that another Sauerstoffatom makes chloro propylene epoxidation.Reacted the transformation efficiency about 30% of propenyl chloride, the selectivity about 85% of epoxy chloropropane 5 hours～6 hours, though this technology can reach the direct epoxidised purpose of propenyl chloride, but because its selectivity is low, compare progress with old technology not obvious, still has a large amount of by products.In addition, because with an organic solvent, also making, process separates the relative complex that becomes.Therefore, we think that this technology has suitable distance from industrialization.
2000, Beijing Shi Keyuan applied for the patent (CN 1534030A) of " a kind of production method of epoxy chloropropane ", was to be that catalyzer is the operational path of oxygenant with the hydrogen peroxide with the HTS.This technology is catalyzer with the HTS, with the hydrogen peroxide is oxygenant, in the presence of a large amount of methyl alcohol (solvent also can be ethanol, propyl alcohol and butanols, acetone or methylethylketone), in 45 ℃～100 ℃ and 0.1MPa～2.0MPa reaction down, the transformation efficiency of propenyl chloride is more than 99%, and the epoxy chloropropane selectivity is more than 96%.List is from the selectivity of the transformation efficiency and the epoxy chloropropane of propenyl chloride, and this technology improves a lot than old technology.But still existing problems, first process is used a large amount of solvents, and the mol ratio of propenyl chloride and solvent is 1: 5～1: 30, better is at 1: 15～1: 20.So just there is a large amount of solvents to reclaim, because distillating recovering solvent makes flow process become relative complex and energy consumption height.Its two epoxy chloropropane hydrolysis that partly generates when being distillating recovering solvent, so that the yield of final epoxy chloropropane reduces, real epoxy chloropropane yield only 90%～92%.It three is the easy inactivations of HTS, and regeneration is complicated.And permanent inactivation easily takes place.
It is big that propylene high-temperature chlorination rule in existing epoxy chloropropane (ECH) production technique has a chlorine consumption height, material consumption height, energy consumption; Equipment corrosion is serious, maintenance cost is high; Produce a large amount of chloride waste water (1 ton of ECH of every production produces 50 tons～60 tons waste water approximately).And the material consumption of allyl acetate method, energy consumption, amount of by-products and wastewater flow rate all descend to some extent, but technical process is longer, and the discharging of equipment corrosion and waste water is still more serious.
Summary of the invention
Order of the present invention aims to provide a kind of work simplification, and technical process is short, can reduce production costs effectively, and energy consumption is low, and is environmentally friendly, and product separates the method for preparing and separating epichlorohydrin by chloropropene epoxidation simply and easily of purifying.
The objective of the invention is to realize by following manner:
Excessive propenyl chloride (ALC) is that oxygenant reacts directly generation epoxy chloropropane under reflux state with the hydrogen peroxide in the presence of phosphate-tungstic acid quaternary ammonium salt and promotor alkylphenol polyoxyethylene; After the gained reaction solution cooling, the solid-phase catalyst of reaction solution recycles after reclaiming, after the oil phase of reaction solution then reclaims unnecessary propenyl chloride by distillation, and the epoxy chloropropane (ECH) that must purify of underpressure distillation again.
At home and abroad in early days and in the document of delivering in the recent period, the selectivity of epoxy chloropropane is all not high enough, as adopting technology in the past propenyl chloride is carried out epoxidation, and the selectivity of epoxy chloropropane is 95.0%～98.0%.Want further to improve the selectivity of epoxy chloropropane, make technology simple again, the flow process weak point then is to be difficult to reach.The present inventor is through hundreds of time experiment, make repeated attempts and find that first the present invention adopts promotor alkylphenol polyoxyethylene (OP) can improve the selectivity of chloropropane effectively, suppress the generation of side reaction, the selectivity of epoxy chloropropane is brought up to more than 99%.The contriver think the add-on of OP with 0.01 times～0.2 times of the hydrogen peroxide quality for preferable; Preferably select 0.01 times～0.1 times.
Former technology is when epoxidation reaction, and must add alkyl chloride such as ethylene dichloride, chloroform is solvent.Comprise that patent CN1155587C, CN 1534030A all need to add in addition other solvent, this just all makes the separate complex of these technological reaction products, and energy consumption increases, and technical process is long, and industrial investment also increases, and is very unfavorable to the reduction product cost.And the present invention adopts propenyl chloride (ALC) excessive, can steam the excess chlorine propylene after the reaction, and returns reaction usefulness, like this with self as solvent, simplified technology and technical process, and do not had the subsequent technique that separates other solvent again.
The present invention is by successfully joining promotor alkylphenol polyoxyethylene (OP) in the epoxy chloropropane technology, and adopt excessive propenyl chloride as raw material and the solvent of self, more than the two combination well, make whole process flow shorten widely, and the selectivity that has improved ECH has effectively suppressed the product of side reaction, the purification of favourable reaction product and separation, can further reclaim catalyzer well in the subsequent technique, and, carry out the effectively purification of underpressure distillation again with ECH by behind the unnecessary ALC of fractionation by distillation.Have only a small amount of waste water to produce in the technology.Reasonable, the simple and environmental protection of operational path, industrial prospect is also very good.
Contriver research thinks that catalyst levels is big more in the technology of the present invention, and it is short more to react the fast more time.For ease of industrial application, the contriver think catalyzer with 0.2 times～1.5 times of the hydrogen peroxide quality for preferable; Preferably select 0.4 times～1.0 times.
Usually, excessive 2 times～4 times of propenyl chloride, i.e. hydrogen peroxide: the propenyl chloride mol ratio be 1: 2～1: 4 for preferable.
Quaternary ammonium salt in the described phosphate-tungstic acid quaternary ammonium salt can be that chlorine (bromine) is changed ammonium, benzyl triethyl ammonium chlorine (bromine) change ammonium, benzyl trimethyl chlorine (bromine) change ammonium, benzyl tributyl chlorine (bromine) change ammonium or phenyl tributyl chlorine (bromine) change ammonium etc. for heptadecyl chloride (bromine) change ammonium, chlorine (bromine) for octadecyl chloride (bromine) for Cetyl Chloride (bromine) change ammonium, chlorine (bromine) for cetyl pyridinium, chlorine (bromine).And the heteropolyanion that plays catalytic activity in the reaction is { PO
4[WO (O
2)
2]
4}
3-
For the direct epoxidation of propenyl chloride, used hydrogen peroxide concentration is high more good more.The contriver has generally selected the hydrogen peroxide more than 50% or 50%.
Along with the raising of temperature of reaction, reaction rate accelerates.General temperature of reaction is controlled at 30 ℃～65 ℃, best 40 ℃～55 ℃.The propenyl chloride transformation efficiency should get 20%～50%, the reaction times be 0.5 hour～5 hours preferable.
Owing to contain catalyzer in the separated object oil phase (being organic phase), in order to save cost, reclaim catalyzer as much as possible, top temperature is no more than 80 ℃ in distillation propenyl chloride (ALC) and underpressure distillation purification epoxy chloropropane (ECH) process.
It is 10 ℃～80 ℃ that unnecessary propenyl chloride controlled temperature is reclaimed in distillation, and 20 ℃～70 ℃ is good.
The pressure-controlling of the epoxy chloropropane that underpressure distillation must be purified is at (10～400) * 133.3Pa.
In addition, to discharge 50 tons～60 tons waste water, cause serious environmental pollution with respect to former 1 ton of ECH of the every production of old technology propylene high-temperature chlorination process.Technology of the present invention has then reduced sewage emissions to greatest extent, and the present invention has only a small amount of waste water to discharge in the chloro propylene epoxidation stage, and 1 ton of ECH of every production only need discharge 0.6 ton waste water.Reclaiming ALC does not then have waste water, waste gas and waste residue to discharge, and vacuum pump has micro-tail gas during underpressure distillation, and product per ton discharges 10 kilograms～15 kilograms organism (high boiling substance is mainly 3-chloro-1, the 2-propylene glycol) approximately.
The phosphate-tungstic acid quaternary ammonium salt that the present invention adopts can be recycled in subsequent process, and the rate of recovery is more than 98%, and activity of such catalysts can satisfy the reaction requirement fully.
In sum, the present invention is with respect to original technology, its whole technology has higher innovation, and adopts promotor alkylphenol polyoxyethylene (OP) can improve the selectivity of epoxy chloropropane well first, by excessive propenyl chloride, promptly make reaction raw materials again as solvent, can simplify follow-up separation process well, whole production technology is very simple again, and industrial investment is few, farthest cutting down the consumption of energy, is a kind of environment amenable comprehensive green production process.
Embodiment
Embodiments of the invention are intended to the present invention is described and should not be construed as limitation of the invention further.
Embodiment 1: the propenyl chloride (ALC) of 500 gram content 98%, the hydrogen peroxide and cocatalyst alkylphenol polyoxyethylene (OP) 5 grams of 170 grams 50% are dropped in 1000 milliliters of there-necked flasks, stir and add 40 gram phosphate-tungstic acid (three) cetyl pyridiniums down, and slowly be warmed up to 40 ℃ stop the heating, react under reflux state, the still temperature reaches 55 ℃ after 60 minutes, and backflow stops, be cooled to still liquid below 5 ℃ this moment, static, tell liquid, solid, solid catalyst can continue on for reaction.Liquid is layering in separating funnel, the upper strata is a water, lower floor is the mixture (oil phase) of epoxy chloropropane and propenyl chloride, abandon it behind the water sampling, collect oil phase through gas chromatographic analysis, oil phase consists of: ALC56.2%, ECH42.2%, by product 1.6%, aqueous phase contain ALC0.29%, ECH2.5%, by product 1.8%, and the aqueous phase hydrogen peroxide content is 0.06%.
Epoxidation gained oil Hunan (ALC56.2%, ECH42.2%, by product 1.6%) is added in 5000 milliliters of there-necked flasks, add thermal rectification under the normal pressure, the control reflux ratio is 1, and ALC is reclaimed in top 45 ℃～46 ℃ extraction of temperature.Product in the middle of gathering when treating the top temperature greater than 46 ℃.Treat that the still temperature reaches 78 ℃ and stops heating, when cooling to 30 ℃～40 ℃, restart vacuum pump, under overbottom pressure (200～300) * 133.3Pa, product in the middle of steaming, treat that top sample analyzes ECH content and reach 96% o'clock extraction ECH, and the control reflux ratio is 1, overbottom pressure (10～50) * 133.3Pa, the still temperature is lower than 80 ℃, treat that still liquid stops heating when being about 300 milliliters, reinforced again after the cooling (middle product can be used as reinforced adding together) repeats aforementioned operation.Drop into oil phase 6900 gram altogether, reclaim the ALC of 3801 grams 98.6%, product in the middle of reclaiming (ALC36.5%, ECH63.4%) 192 grams, altogether 2870 restrain 99.5% ECH.
Embodiment 2: propenyl chloride, hydrogen peroxide, cocatalyst are pressed embodiment 1 and are added, and catalyzer is that embodiment 1 reclaims, and reacts epoxy chloropropane selectivity 99.6% 90 minutes.
Embodiment 3: it is identical with embodiment 1 to fill a prescription, and catalyzer is from the recycling of underpressure distillation epoxy chloropropane tower still, reacts epoxy chloropropane selectivity 98.8% 100 minutes.
Embodiment 4: the hydrogen peroxide of propenyl chloride 500 gram, 130 grams 50%, promotor 5 grams, other step are with embodiment 1, epoxy chloropropane selectivity 99.9%.
Embodiment 5～9: other step changes the consumption of promotor consumption with embodiment 1, and experimental result is as follows:
| Embodiment | Promotor consumption (in the multiple of hydrogen peroxide quality) | ALC transformation efficiency (mol%) | ECH selectivity (mol%) |
| Embodiment 5 | 0.01 | 34.8 | 99.5 |
| Embodiment 6 | 0.05 | 34.9 | 99.7 |
| Embodiment 7 | 0.10 | 35.0 | 99.4 |
| Embodiment 8 | 0.15 | 35.1 | 99.5 |
| Embodiment 9 | 0.2 | 34.8 | 99.0 |
Embodiment 10～16: other step changes the consumption and the reaction times of catalyst levels with embodiment 1, and experimental result is as follows:
| Embodiment | Catalyst levels (in the multiple of hydrogen peroxide quality) | Reaction times (h) | Transformation efficiency (mol%) | ECH selectivity (mol%) |
| Embodiment 10 | 0.2 | 5.0 | 36.4 | 95.8 |
| Embodiment 11 | 0.25 | 3.5 | 36.4 | 98.9 |
| Embodiment 12 | 1.2 | 0.6 | 36.5 | 99.4 |
| Embodiment 13 | 1.5 | 0.8 | 36.3 | 99.1 |
| Embodiment 14 | 0.5 | 1.5 | 36.4 | 99.6 |
| Embodiment 15 | 0.8 | 1.0 | 36.5 | 99.5 |
| Embodiment 16 | 1.0 | 0.8 | 36.3 | 99.4 |
Embodiment 17～19: other step changes the kind of catalyzer with embodiment 1, and experimental result is as follows:
| Embodiment | The kind of catalyzer | Transformation efficiency (mol%) | ECH selectivity (mol%) |
| Embodiment 17 | Phospho-wolframic acid (three) hexadecyl trimethylamine | 38.8 | 99.0 |
| Embodiment 18 | Phospho-wolframic acid (three) heptadecyl Trimethylamine 99 | 38.9 | 98.5 |
| Embodiment 19 | Phospho-wolframic acid (three) benzyl triethyl ammonium Trimethylamine 99 | 38.8 | 98.2 |
Claims (9)
1, the method for preparing and separating epichlorohydrin by chloropropene epoxidation, it is characterized in that: excessive propenyl chloride is that oxygenant reacts directly generation epoxy chloropropane under reflux state with the hydrogen peroxide in the presence of phosphate-tungstic acid quaternary ammonium salt and promotor alkylphenol polyoxyethylene; After the gained reaction solution cooling, the solid-phase catalyst of reaction solution recycles after reclaiming, after the oil phase of reaction solution then reclaims unnecessary propenyl chloride by distillation, and the epoxy chloropropane that must purify of underpressure distillation again.
2, the method for preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: the add-on of promotor alkylphenol polyoxyethylene is 0.01 times～0.2 times of hydrogen peroxide quality.
3, the method for preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: catalyzer is 0.2 times～1.5 times of hydrogen peroxide quality.
4, the method for preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: temperature of reaction is controlled at 30-65 ℃, and the reaction times is 0.5-5h.
5, the method for the described preparing and separating epichlorohydrin by chloropropene epoxidation of claim 4 is characterized in that: hydrogen peroxide: the propenyl chloride mol ratio is 1: 2～4.
6, according to the method for each described preparing and separating epichlorohydrin by chloropropene epoxidation of claim 1-5, it is characterized in that: propenyl chloride transformation efficiency 30-50%.
7, the method for preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: top temperature is no more than 80 ℃ in distillation propenyl chloride and underpressure distillation purification epoxy chloropropane.
The method of 8 preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: it is 10-80 ℃ that unnecessary propenyl chloride temperature is reclaimed in distillation.
9, the method for preparing and separating epichlorohydrin by chloropropene epoxidation according to claim 1 is characterized in that: the pressure-controlling of the epoxy chloropropane that underpressure distillation must be purified is at 10 * 133.3Pa-400 * 133.3Pa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8481765B2 (en) | 2008-03-17 | 2013-07-09 | Momentive Specialty Chemicals Inc. | Method for the production of epichlorohydrin |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
| US8802873B2 (en) | 2008-08-01 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for the manufacture of epichlorohydrin |
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| CN101880263B (en) * | 2009-05-09 | 2012-07-11 | 中国石油化工集团公司 | Preparation method of epichlorohydrin |
| CN102309993A (en) * | 2010-07-04 | 2012-01-11 | 中国石油化工集团公司 | Method for recycling heteropolyacid quaternary ammonium salt catalyst |
| EP2796452A1 (en) | 2013-04-23 | 2014-10-29 | Momentive Specialty Chemicals Research Belgium S.A. | Process for removal of 1,2-epoxy-5-hexene from epichlorohydrin |
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| CN109395754B (en) * | 2018-10-29 | 2021-06-25 | 江苏扬农化工集团有限公司 | Method for recovering heteropoly acid catalyst from chloropropene epoxidation oil layer |
| CN112521348B (en) * | 2020-12-03 | 2022-06-28 | 山东泰和水处理科技股份有限公司 | Method for synthesizing epoxy succinic acid by maleic anhydride catalytic epoxidation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8481765B2 (en) | 2008-03-17 | 2013-07-09 | Momentive Specialty Chemicals Inc. | Method for the production of epichlorohydrin |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
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| CN101016280A (en) | 2007-08-15 |
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