CN105153069A - Method for preparing epoxy chloropropane - Google Patents
Method for preparing epoxy chloropropane Download PDFInfo
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- CN105153069A CN105153069A CN201510608843.4A CN201510608843A CN105153069A CN 105153069 A CN105153069 A CN 105153069A CN 201510608843 A CN201510608843 A CN 201510608843A CN 105153069 A CN105153069 A CN 105153069A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing epoxy chloropropane. Material dichloropropanol and carrier gas together enter a fixed bed cyclizing device filled with a catalyst after dichloropropanol is gasified, a gas-phase hydrogen chloride removal and cyclization reaction is carried out in the temperature range of 200-450 DEG C, hydrogen chloride and product epoxy propane are separated through a condensation pipe, and the catalyst is selected from one of a molecular sieve HY, Hbeta, HZSM-5 and sodalite. The optimal catalyst is a solid base catalyst obtained by loading alkaline earth metal oxide on a cation-type molecular sieve. Production cost is low, side effects are few, the conversion rate of the reaction is increased, and product selectivity is improved. By means of a gas-phase cyclizing heterogeneous reaction system, a series of defects, for example, three wastes are difficult to treat, caused by a liquid-liquid homogeneous reaction are successfully avoided, and the obtained product is easy to separate.
Description
Technical field
The present invention relates to a kind of method preparing epoxy chloropropane, specifically relate to the method that 1,3-bis-chloro-2-propyl alcohol gas phase catalysis prepares epoxy chloropropane.
Background technology
Epoxy chloropropane (Epichlorohydrin), alias table chloropharin is a kind of important Organic Chemicals and synthetic intermediate, and in epoxy compounds, the output of epoxy chloropropane occupies the 3rd, is only second to oxyethane and propylene oxide.Throughput about 248.4 ten thousand t/a of world's epoxy chloropropane in 2012, China's throughput is 1,060,000 t/a.In recent years, China has developed into epoxy chloropropane producing country maximum in the world, and the degree of self-sufficiency improves constantly.Epoxy chloropropane purposes is very extensive, mainly for the production of epoxy resin, synthesis nitroglycerine explosive, glass reinforced plastic, electrical isolation product, multiple product such as (contracting) glycerol derivative, chlorohydrin rubber etc., and produce chemical stabilizer, chemical dyestuff and water conditioner etc., can be used as the solvent of cellulose ester, resin, ether of cellulose simultaneously.At present, the method for industrial production epoxy chloropropane mainly contains three kinds: propylene high-temperature chlorination process, acetate propylene ester process and take glycerine as the glycerine method of raw material.In the production technique of these three kinds of epoxy chloropropane, what final step saponification process generally adopted is 1, under calcium hydroxide or sodium hydroxide solution effect, there is saponification reaction and generate epoxy chloropropane in the chloro-2-propyl alcohol (1,3-Dichloro-2-propanol) of 3-bis-.Its reaction formation is liquid-liquid homogeneous reaction, and saponification reaction needs excessive alkali lye, create the trade effluent that a large amount of reluctant saltiness is high, and by product is more in this process, and the purification of product needs to improve further.
Summary of the invention
It is few that the technical problem to be solved in the present invention is to provide a kind of side reaction, the segregative method preparing epoxy chloropropane of product.
For solving above technical problem, the technical solution used in the present invention is: a kind of method preparing epoxy chloropropane, after the gasification of material dichlorohydrine, enter together with carrier gas and be filled with in the fixed bed cyclisation device of catalyzer, in 200 DEG C ~ 450 DEG C temperature ranges, carry out gas phase removal hydrogenchloride cyclization, through prolong separating hydrogen chloride and product propene oxide, described catalyzer is selected from the one of molecular sieve HY, H β, HZSM-5 and sodalite.
Reaction formation in aforesaid method is gas-solid heterogeneous reaction system, the by product that reaction generates is hydrogenchloride, can be used as the chlorine source recycle preparing propylene dichloride, it is a kind of environmentally friendly synthetic route, effectively can avoid the problem easily producing waste liquid, waste residue in traditional technology, product is more easily separated.
As preferred technical scheme, described catalyzer is the Cation molecule sieve obtained after molecular sieve is carried out cationic exchange, can improve the transformation efficiency of reaction, selectivity and yield.Preferably, the molecular sieve positively charged ion carried out in cationic exchange is alkalimetal ion, usually uses K
+or Na
+ion.
As preferred technical scheme, described catalyzer is the solid base catalyst that supported alkaline earth metal oxide compound obtains on Cation molecule sieve.The solid base catalyst that the program provides, has high catalytic activity, can improve the transformation efficiency of reaction, the selectivity of product, yield further.Preferably, alkaline earth metal oxide is the one in MgO, CaO and BaO.Further preferred scheme is that to make particle diameter be 60 ~ 100 object particles to described solid base catalyst.
Preferred solid base catalyst preparation method provided by the invention is: HY, H β, HZSM-5 or sodalite are carried out cationic exchange, carrier is made with Cation molecule sieve, the presoma of alkaline earth metal oxide is dissolved in the distilled water of the saturated water adsorptive value volume being equivalent to carrier and makes solution, again support powder is added in above-mentioned solution, dry after leaving standstill after stirring and evenly mixing, and calcine in air atmosphere, obtain solid base catalyst powder, then pressed powder is screened solid base catalyst particle.
As preferred technology incidence of criminal offenses, described carrier gas is nitrogen, argon gas or helium, and flow rate of carrier gas is 100 ~ 300ml/min.
Preferred cyclization temperature is 300 DEG C ~ 400 DEG C; .
As preferred technical scheme, the gasification temperature of material dichlorohydrine is 60 DEG C ~ 120 DEG C.
The beneficial effect of the epoxy chloropropane production method that the present invention proposes is: (1) this solid base catalyst catalytic activity is high, and production cost is little, and side reaction is few, improves the transformation efficiency of reaction and the selectivity of product.(2) " three wastes " that employing liquid-liquid homogeneous reaction brings are difficult to a series of defects such as process to adopt gas phase cyclisation heterogeneous reaction system successfully avoid, and the product obtained also easily is separated.(3) hydrogenchloride produced in reaction process can be used as the chlorine source of preparing dichlorohydrine and recycles, and effectively utilizes hydrogenchloride, not only economy but also environmental protection.(4) solid base catalyst regenerating easily and can not etching apparatus, should use safety, cheap, operational condition is gentle.(5) technique is simple, and flow process is short, and energy consumption is low, and total investment expenses are relatively little.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device that the present invention adopts.
In figure, 1. flow stabilizing valve 2. spinner-type flowmeter 3. T-valve 4. saturex 5. oil bath 6. tube furnace 7. beds 8. prolong 9. scrubbing bottle 10. automatic temperature control instrument.
Embodiment
Carrier gas (nitrogen, argon gas or helium) is through flow stabilizing valve (1), spinner-type flowmeter (2), T-valve (3) enters in saturex (4), carry dichlorohydrine gas to flow out from saturex (4) upper end, dichlorohydrine gas gasifies in saturex, the beds (7) entering into tube furnace (6) afterwards carries out gas-solid heterogeneous catalysis cyclization, and product is collected at prolong (8) after condensation.
The present invention is further described for the following examples, but not thereby limiting the invention.
Embodiment 1
The present embodiment illustrates reaction process when catalyzer is 5CaO/80NaZSM-5 (quality of the CaO of load is 5%, Si/Al=80 of NaZSM-5 quality) and result.
(1) first preparing 500ml concentration is the NaNO of 1mol/L
3solution, then the HZSM-5(Si/Al=80 getting 3g) molecular sieve powder is dissolved in enough above-mentioned solution, and stir 2 ~ 3h under room temperature condition, repeat 4 times, after suction filtration, drying, obtain 80NaZSM-5 sample in 550 DEG C of roasting 6h.
(2) by the Ca (NO of 0.4211g
3)
24H
2o is dissolved in and is equivalent in the saturated water adsorptive value volume 2.5ml distilled water of 80NaZSM-5, then is mixed in above-mentioned solution by the 80NaZSM-5 powder of 2g, after drying, in 550 DEG C of air, calcines 7h, obtains 5CaO/80NaZSM-5 catalyst fines.
(3) by catalyzer powder compressing machine compressing tablet obtained above, pressure is 6MPa, dwell time 1min, and then to filter out diameter be 60 ~ 80 molecules of interest sieve particle 0.5g being ground.
(4) the 0.5g pellet type catalyst screened is loaded in reaction tubes (Ф 8mm × 1mm × 250mm), after the gasification of material dichlorohydrine, enter together with carrier gas nitrogen and be filled with in the fixed bed cyclisation device of particulate solid alkaline catalysts, respectively at 300 DEG C, 330 DEG C, 360 DEG C, vapor phase cyclization reaction is carried out at 390 DEG C of temperature, collect after the condensation of product epoxy chloropropane, wherein the temperature of saturex is 100 DEG C, carrier gas flux is 100ml/min, and collected product is through gas chromatographic analysis, and its result is as follows:
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 99.3 | 91.3 | 90.6 |
| 330 | 99.6 | 93.8 | 93.5 |
| 360 | 100 | 93.4 | 93.4 |
| 390 | 100 | 89.9 | 89.9 |
Embodiment 2
The present embodiment illustrates reaction process when catalyzer is HY and result.
By HY molecular sieve powder compressing tablet, filtering out diameter is 80 ~ 100 object HY sieve particle 0.3g, the HY sieve particle weighed up is loaded in reaction tubes (Ф 8mm × 1mm × 250mm), the temperature of saturex is 60 DEG C, carrier gas flux is 200ml/min, and other steps are identical with (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 32.0 | 83.1 | 26.3 |
| 330 | 32.4 | 80.0 | 26.0 |
| 360 | 32.9 | 76.0 | 25.1 |
| 390 | 18.1 | 61.6 | 11.1 |
Embodiment 3
It is 10%, Si/Al=25 of NaZSM-5 quality in the quality that catalyzer is the MgO of 10MgO/25NaZSM-5(load that the present embodiment illustrates) time reaction process and result.
HZSM-5(Si/Al=25) the Na exchange process of molecular sieve is identical with (1) of embodiment 1, by the Mg (NO of 1.2722g
3)
26H
2o is dissolved in and is equivalent to, in the saturated water adsorptive value volume 2.5ml distilled water of 25NaZSM-5, be mixed in above-mentioned solution, after its drying, in 550 DEG C of air, calcine the 25NaZSM-5 powder of 2g 7h, obtain 10MgO/25NaZSM-5 catalyst fines.Other steps are identical with step (3) (4) in embodiment 1.Its result is as follows:
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 91.7 | 95.3 | 87.4 |
| 330 | 97.1 | 96.8 | 93.9 |
| 360 | 98.2 | 96.6 | 94.9 |
| 390 | 62.7 | 93.5 | 58.6 |
Embodiment 4
The present embodiment illustrates reaction process when catalyzer is KY and result.
(1) prepare the KCl solution that 500ml concentration is 1mol/L, the HY molecular sieve getting 3g is dissolved in enough above-mentioned solution, and stirred at ambient temperature 2h ~ 3h, repeats 4 times by aforesaid operations, after suction filtration, drying, in 550 DEG C of roasting 6h, obtains KY sieve sample.
(2) by KY molecular sieve powder compressing tablet, filtering out diameter is 60 ~ 80 molecules of interest sieve particle 0.3g, the KY molecular sieve weighed up is loaded in reaction tubes (Ф 8mm × 1mm × 250mm), the temperature of its saturex is 120 DEG C, carrier gas flux is 200ml/min, and other steps are identical with (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 60.0 | 83.8 | 50.4 |
| 330 | 44.1 | 79.0 | 34.9 |
| 360 | 54.1 | 84.1 | 45.5 |
| 390 | 57.0 | 82.4 | 47.0 |
Embodiment 5
The present embodiment illustrates reaction process when catalyzer is K β and result.
The potassium ion exchange process of H β is with the step (1) in embodiment 4, by K beta-molecular sieve pressed powder, filtering out diameter is 60 ~ 80 molecules of interest sieve particle 0.3g, loaded in reaction tubes (Ф 8mm × 1mm × 250mm) by the K beta-molecular sieve weighed up, other steps are with the step (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 38.9 | 75.0 | 29.2 |
| 330 | 63.2 | 84.8 | 53.6 |
| 360 | 88.9 | 90.2 | 80.2 |
| 390 | 95.8 | 89.4 | 85.6 |
Embodiment 6
The present embodiment illustrates reaction process when catalyzer is KZSM-5 (Si/Al=38) and result.
The potassium ion exchange process of HZSM-5 (Si/Al=38) is with the step (1) in embodiment 4, obtain KZSM-5 sieve sample, by KZSM-5 molecular sieve powder compressing tablet, filtering out diameter is 60 ~ 80 object KZSM-5 sieve particle 0.3g, loaded in reaction tubes (Ф 8mm × 1mm × 250mm) by the KZSM-5 molecular sieve weighed up, other steps are with (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 300 | 89.8 | 91.1 | 81.7 |
| 330 | 99.2 | 95.0 | 94.2 |
| 360 | 99.5 | 95.1 | 94.6 |
| 390 | 99.7 | 94.3 | 94.0 |
Embodiment 7
It is 2%, Si/Al=80 of NaZSM-5 quality in the quality that catalyzer is the BaO of 2BaO/80NaZSM-5(load that the present embodiment illustrates) time reaction process and result.
HZSM-5(Si/Al=80) sodium exchange process, with the step (1) in embodiment 1, obtains 80NaZSM-5 sieve sample, by the Ba (NO of 0.0682g
3)
2be dissolved in and be equivalent in the saturated water adsorptive value volume 2.5ml distilled water of 80NaZSM-5, then the 80NaZSM-5 powder of 2g is mixed in above-mentioned solution, after drying, in 550 DEG C of air, calcine 7h, obtain 2BaO/80NaZSM-5 catalyst fines.Other steps are with step (3) (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selection rate/% | Yield/% |
| 300 | 92.4 | 90.1 | 83.3 |
| 330 | 94.7 | 86.7 | 82.1 |
| 360 | 99.5 | 82.5 | 82.1 |
| 390 | 99.8 | 78.3 | 78.2 |
Embodiment 8
The present embodiment illustrates reaction process when catalyzer is sodalite and result.
By sodalite molecular sieve powder compressing tablet, filtering out diameter is 60 ~ 80 object particle 0.5g, the sodalite particle weighed up is loaded in reaction tubes (Ф 8mm × 1mm × 250mm), respectively at 200 DEG C, 250 DEG C, 300 DEG C, react at 350 DEG C of temperature, other steps are with the step (4) in embodiment 1.
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 200 | 14.3 | 79.4 | 11.4 |
| 250 | 61.0 | 93.0 | 56.7 |
| 300 | 89.0 | 93.6 | 83.4 |
| 350 | 98.8 | 94.8 | 93.6 |
Embodiment 9
The present embodiment illustrates when different flow rate of carrier gas, NaZSM-5(Si/Al=50) reaction process under catalysis and result.
HZSM-5(Si/Al=50) sodium exchange process is with the step (1) in embodiment 1, obtain 50NaZSM-5 sieve sample, by 50NaZSM-5 molecular sieve powder compressing tablet, filtering out diameter is 60 ~ 80 object particle 0.5g, the 50NaZSM-5 particle weighed up is loaded in reaction tubes, flow rate of carrier gas is respectively at 150ml/min, 200ml/min; Temperature of reaction is 330 DEG C, reacts at 360 DEG C, and implementation step is with (4) in embodiment 1.Its result is as follows:
Embodiment 10
The present embodiment illustrates that catalyzer be the quality of the MgO of 2MgO/80NaZSM-5(load is 2%, Si/Al=80 of NaZSM-5 quality) reaction process under catalysis and result.
HZSM-5(Si/Al=80) Na of molecular sieve
+exchange process is identical with the step (1) of embodiment 1, by the Mg (NO of 0.2544g
3)
26H
2o is dissolved in and is equivalent to, in the saturated water adsorptive value volume 2.5ml distilled water of 80NaZSM-5, be mixed in above-mentioned solution, after its drying, in 550 DEG C of air, calcine the 80NaZSM-5 powder of 1.9920g 7h, obtain 2MgO/80NaZSM-5 catalyst fines.Except temperature of reaction is 200 DEG C, 330 DEG C, outside 450 DEG C, other steps are identical with step (3) (4) in embodiment 1.Its result is as follows:
| Temperature (DEG C) | Transformation efficiency/% | Selectivity/% | Yield/% |
| 200 | 46.5 | 98.4 | 45.8 |
| 330 | 98.7 | 94.4 | 93.2 |
| 450 | 83.4 | 67.5 | 56.3 |
Embodiment 11
The present embodiment explanation catalyzer is the quality of the MgO of 2MgO/80NaZSM-5(load is 2%, Si/Al=80 of NaZSM-5 quality), reaction process when flow rate of carrier gas is 300ml/min and result.
2MgO/80NaZSM-5(Si/Al=80) preparation of sample is with the 2MgO/80NaZSM-5(Si/Al=80 in embodiment 10) preparation identical, by this sample compressing tablet, the particle diameter filtering out 0.5g is 60 ~ 80 molecules of interest sieve particles, be loaded in reaction tubes (Ф 8mm × 1mm × 250mm), vapor phase cyclization reaction is carried out at 300 DEG C of temperature, carrier gas flux is 300ml/min, the temperature of saturex is 100 DEG C, collect after the condensation of product epoxy chloropropane, wherein product is through chromatography of gases analysis, obtaining its transformation efficiency is 73.3%, selectivity is 93.4%, yield is 68.4%.
Claims (10)
1. prepare the method for epoxy chloropropane for one kind, it is characterized in that: after the gasification of material dichlorohydrine, enter together with carrier gas and be filled with in the fixed bed cyclisation device of catalyzer, in 200 DEG C ~ 450 DEG C temperature ranges, carry out gas phase removal hydrogenchloride cyclization, through prolong separating hydrogen chloride and product propene oxide, described catalyzer is selected from the one of molecular sieve HY, H β, HZSM-5 and sodalite.
2. method according to claim 1, is characterized in that: described catalyzer is the Cation molecule sieve obtained after molecular sieve is carried out cationic exchange.
3. method according to claim 2, is characterized in that: the molecular sieve positively charged ion carried out in cationic exchange is alkalimetal ion.
4. method according to claim 2, is characterized in that: described catalyzer is the solid base catalyst that supported alkaline earth metal oxide compound obtains on Cation molecule sieve.
5. method according to claim 4, is characterized in that: described alkaline earth metal oxide is the one in MgO, CaO and BaO.
6. the method according to claim 4 or 5, is characterized in that: it is 60 ~ 100 object particles that described solid base catalyst makes particle diameter.
7. method according to claim 6, it is characterized in that: HY, H β, HZSM-5 or sodalite are carried out cationic exchange, carrier is made with Cation molecule sieve, the presoma of alkaline earth metal oxide is dissolved in the distilled water of the saturated water adsorptive value volume being equivalent to carrier and makes solution, again support powder is added in above-mentioned solution, dry after leaving standstill after stirring and evenly mixing, and calcine in air atmosphere, obtain solid base catalyst powder, then pressed powder is screened solid base catalyst particle.
8. method according to claim 1, is characterized in that: described carrier gas is nitrogen, argon gas or helium, and flow rate of carrier gas is 100 ~ 300ml/min.
9. method according to claim 1, is characterized in that: described cyclization temperature is 300 DEG C ~ 400 DEG C.
10. method according to claim 1, is characterized in that: the gasification temperature of material dichlorohydrine is 60 DEG C ~ 120 DEG C.
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|---|---|---|---|
| CN201510608843.4A CN105153069B (en) | 2015-09-23 | 2015-09-23 | Method for preparing epoxy chloropropane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586390A (en) * | 2018-07-04 | 2018-09-28 | 山东民基化工有限公司 | The method that dichlorohydrin prepares epoxychloropropane |
| CN114507197A (en) * | 2021-12-28 | 2022-05-17 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
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| CN103539763A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Reaction separation coupling technology for continuously preparing epoxy chloropropane from dichloropropanol |
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2015
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| CN103539763A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Reaction separation coupling technology for continuously preparing epoxy chloropropane from dichloropropanol |
Non-Patent Citations (2)
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| 李贤宇等: "二氯丙醇合成环氧氯丙烷反应催化剂活性评价及其影响因素研究", 《天津化工》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586390A (en) * | 2018-07-04 | 2018-09-28 | 山东民基化工有限公司 | The method that dichlorohydrin prepares epoxychloropropane |
| CN108586390B (en) * | 2018-07-04 | 2020-06-23 | 山东民基新材料科技有限公司 | Method for preparing epoxy chloropropane from dichloropropanol |
| CN114507197A (en) * | 2021-12-28 | 2022-05-17 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
| CN114507197B (en) * | 2021-12-28 | 2024-01-26 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
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