CN111574481A - Method for preparing epichlorohydrin - Google Patents
Method for preparing epichlorohydrin Download PDFInfo
- Publication number
- CN111574481A CN111574481A CN202010479299.9A CN202010479299A CN111574481A CN 111574481 A CN111574481 A CN 111574481A CN 202010479299 A CN202010479299 A CN 202010479299A CN 111574481 A CN111574481 A CN 111574481A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- chloropropene
- solvent
- surfactant
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 102
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 4
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 229920000053 polysorbate 80 Polymers 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- SPHPVCBZNTZISK-UHFFFAOYSA-N 4-ethyl-2-(4-methylphenyl)-5,6-dihydro-1,3-selenazin-4-ol Chemical compound CCC1(O)CC[Se]C(C=2C=CC(C)=CC=2)=N1 SPHPVCBZNTZISK-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The present invention provides a process for preparing epichlorohydrin, the process comprising: chloropropene is used as a raw material, hydrogen peroxide is used as an oxidant, a solvent and a surfactant are added, and the reaction is carried out in a fixed bed catalytic reactor. The method provided by the invention enables hydrogen peroxide and chloropropene to react in one step in a fixed bed catalytic reactor to prepare epoxy chloropropane through the catalytic action and the promotion action of the solvent and the surfactant, and the catalyst is easy to separate, so that the green and safe production of epoxy chloropropane with high efficiency, low energy consumption, low toxicity, low by-product and no pollution can be realized, and the method can completely replace the traditional chlorohydrination method for producing epoxy chloropropane.
Description
Technical Field
The invention relates to the field of preparation of organic chemical intermediates, and in particular relates to a method for preparing epichlorohydrin.
Background
Epichlorohydrin is an important organic chemical intermediate and is mainly used for producing epoxy resin. Currently, the industrial preparation of epichlorohydrin mainly adopts a chlorohydrin method, chloropropene, chlorine and water are subjected to chlorohydrination reaction to prepare dichloropropanol, and then the dichloropropanol is further saponified to obtain epichlorohydrin. In the chlorohydrination reaction, chlorine is used as an oxidant and a chlorine source, water is used for providing hydroxyl, the reaction mechanism is that hypochlorous acid generated by the reaction of the chlorine and the water oxidizes a double bond of chloropropene, electrons on the double bond are transferred to a chlorine atom, the chlorine atom is added to the double bond, and then the hydroxyl nucleophilically attacks another carbon atom of the double bond to generate dichloropropanol.
However, the chlorohydrin method uses highly toxic chlorine as a raw material, and has low safety; the oxidation by-product hydrochloric acid can cause low atom utilization rate of chlorohydrination reaction, so that the yield of epoxy chloropropane is low; chlorine has active chemical property, is easy to generate side reaction and generates more byproducts; the direct addition reaction with chloropropene can generate low-value trichloropropane, and in order to control the concentration of a target product, a large amount of water is required to dilute the concentration of chlorine in a reaction system, so that the energy consumption in the saponification separation process is high, and each ton of epoxy chloropropane generates waste water and waste residue which are difficult to treat, thereby polluting the environment.
Disclosure of Invention
The embodiment of the invention provides a method for preparing epichlorohydrin, which is characterized in that hydrogen peroxide and chloropropene are reacted in one step to prepare epichlorohydrin through catalysis and promotion of a solvent and a surfactant, so that the effects of greenness, high efficiency and energy conservation are achieved.
The embodiment of the invention provides a method for preparing epichlorohydrin, which comprises the following steps:
chloropropene is used as a raw material, hydrogen peroxide is used as an oxidant, a solvent and a surfactant are added, and the reaction is carried out in a fixed bed catalytic reactor.
Compared with the prior art, the invention has the beneficial effects that:
the method provided by the invention can realize green and safe production of epoxy chloropropane with high efficiency, low energy consumption, low toxicity, low by-product and no pollution, and can completely replace the traditional chlorohydrin method for producing epoxy chloropropane.
Drawings
Figure 1 is a schematic process flow diagram for preparing epichlorohydrin, which is provided by the embodiment of the invention,
in the figure, 1: a fixed bed catalytic reactor; 2: a separator; 3: a reactor; 4: a surfactant; 5: solvent, hydrogen peroxide and chloropropene; 6: a first product; 7: epichlorohydrin and residual chloropropene; 8: solvent and residual hydrogen peroxide; 9: chloropropene; 10: a second product.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
The embodiment of the invention provides a method for preparing epichlorohydrin, which comprises the following steps:
chloropropene is used as a raw material, hydrogen peroxide is used as an oxidant, a solvent and a surfactant are added, and the reaction is carried out in a fixed bed catalytic reactor.
The reaction can be carried out at normal pressure or elevated pressure.
The solvent may be an alcohol, a ketone, an acid, an ester, or a nitrile, and is preferably a common reagent such as methanol, ethanol, acetone, methyl ethyl ketone, or acetonitrile, and is more preferably methanol. The chloropropene and the hydrogen peroxide are not mutually soluble, and the solubility of the chloropropene and the hydrogen peroxide can be effectively increased by the solvent. The amount of solvent is based on the filling of the reaction bed.
The surfactant may be one or more of an anionic surfactant (e.g. stearic acid, sodium dodecylbenzene sulphonate), a cationic surfactant (e.g. a quaternary ammonium salt), a zwitterionic surfactant (e.g. lecithin, amino acid type, betaine type), a non-ionic surfactant (e.g. fatty acid glyceride, fatty acid sorbitan (span), polysorbate (tween)). The addition of the surfactant can further increase the solubility of chloropropene and hydrogen peroxide and improve the reaction conversion rate; the adsorption and diffusion speed of reactants on the surface of the catalyst can be accelerated, the reaction efficiency is increased, and the service life of the catalyst is prolonged.
Preferably, the surfactant is a non-ionic surfactant, further preferably a combination of span and tween, such as: the combination of span-60 (added in 0.005% -0.5%) and tween-80 (added in 0.005% -0.5%), or the combination of span-80 (added in 0.005% -0.5%) and tween-60 (added in 0.005% -0.5%), or the combination of span-60 (added in 0.005% -0.5%) and tween-60 (added in 0.005% -0.5%), or the combination of span-80 (added in 0.005% -0.5%) and tween-80 (added in 0.005% -0.5%), etc.
In a preferred embodiment of the present invention, the span and the tween are loaded on a certain amount of the carrier, and then the surfactant containing the carrier is added to the reaction system. Wherein, the benzene accounts for 0.005 to 0.5 weight percent of the total amount of the surfactant and the carrier, and the Tween accounts for 0.005 to 0.5 weight percent of the total amount of the surfactant and the carrier. The surfactant containing the carrier accounts for 0.0005 to 0.1 percent of the mass of the reaction system, and preferably 0.005 to 0.05 percent of the mass of the reaction system. The reaction system refers to the sum of chloropropene, hydrogen peroxide and a solvent.
The hydrogen peroxide (hydrogen peroxide) may be pure, but from the viewpoint of safety and economy, an aqueous solution having a concentration of 5% to 90% is preferably used, and an aqueous solution having a concentration of 30% to 70% is more preferably used.
The mol ratio of the chloropropene to the hydrogen peroxide (calculated as pure hydrogen peroxide) is 10:1-1:1, and preferably 3:1-1.5: 1.
The catalyst in the fixed bed catalytic reactor adopts a titanium silicalite molecular sieve, which is a generic name of zeolite with titanium atoms replacing part of silicon atoms in a lattice framework. Such materials are known in the art as titanium-containing zeolites having an MFI topology like ZSM-5 aluminosilicate zeolite, TS-1, MEL topology like ZSM-11 aluminosilicate zeolite, TS-2, and titanium-containing molecular sieves having framework structures isomorphous to mordenite, ZSM-12, MCM-41, MCM-48, and MWW, among others. The titanium-silicon molecular sieve can be purchased commercially or prepared by self. The particle size of the catalyst is 0.1mm to 10cm, preferably 1mm to 3 mm.
When feeding, preferably, the solvent, the hydrogen peroxide and the chloropropene are mixed firstly, and then mixed with the surfactant at the feed inlet of the reactor. The feeding can be carried out by adopting the upper part or the lower part of the reactor and the concurrent flow. A feed space velocity ofCalculated by hydrogen peroxide, is 0.05 to 4 hours-1Preferably 0.1 to 2h-1。
Based on the above embodiment, the method for preparing epichlorohydrin provided by the embodiment of the present invention further includes:
and separating the product of the fixed bed catalytic reactor, introducing the separated solvent and residual hydrogen peroxide into another reactor, and simultaneously introducing chloropropene for reaction.
Specifically, referring to fig. 1, a solvent, hydrogen peroxide and chloropropene 5 and a surfactant 4 are fed into a fixed bed catalytic reactor 1, the chloropropene and the hydrogen peroxide undergo an epoxidation reaction in the fixed bed catalytic reactor 1, and a first product 6 is generated and comprises epichlorohydrin, the solvent, residual chloropropene and residual hydrogen peroxide. Introducing the first product 6 into a separator 2 for separation, extracting the separated epoxy chloropropane and residual chloropropene 7, and further processing to obtain epoxy chloropropane; and introducing the separated solvent and residual hydrogen peroxide 8 into a reactor 3 filled with a catalyst, and introducing chloropropene 9 at the same time, so that catalytic epoxidation reaction is continuously carried out in the reactor 3, and a generated second product 10 comprises epoxy chloropropane, chloropropene, solvent and water, and processing to obtain an epoxy chloropropane product.
Wherein the separator 2 can adopt centrifugal separation or standing separation.
The reactants are difficult to completely react in the reactor, and when the hydrogen peroxide is excessive, a large amount of residues exist, so that the excessive chloropropene is generally adopted, but a small amount of hydrogen peroxide also remains when the chloropropene is excessive, and the residual hydrogen peroxide can be decomposed to generate oxygen during subsequent separation, so that the process risk is increased. In the embodiment of the invention, the hydrogen peroxide in the fixed bed catalytic reactor 1 can only react for 90-95 percent, and 5-10 percent of hydrogen peroxide can be remained. In the embodiment of the invention, the solvent and the residual hydrogen peroxide 8 are added into chloropropene 9, and after further catalytic reaction in the reactor 3, the residual hydrogen peroxide can be reacted completely, namely the second product 10 does not contain hydrogen peroxide, so that unsafe factors of oxygen generated by decomposition of the residual hydrogen peroxide are avoided.
The reason why the hydrogen peroxide can be completely reacted in the reactor 3 of the embodiment of the present invention is that: only 5-10% of residual hydrogen peroxide is left in the first product 6 at the outlet of the fixed bed catalytic reactor 1, and the absolute content of the hydrogen peroxide is low, so that the molar ratio of chloropropene to the hydrogen peroxide in the reactor 3 can reach a large value, the complete reaction is facilitated, and the actual absolute amount of chloropropene is not large. Of course, the hydrogen peroxide can be reacted completely by simultaneously reducing the space velocity and increasing the reaction temperature. Even without using a fixed bed reactor, other reaction forms such as a boiling bed, a slurry bed or a fluidized bed are selected to improve the conversion rate of the hydrogen peroxide and realize the complete reaction of 5 to 10 percent of residual hydrogen peroxide.
Example 1
The embodiment of the invention provides a method for preparing epichlorohydrin, which comprises the following specific steps:
mixing methanol, 30% hydrogen peroxide and chloropropene, wherein the mol ratio of chloropropene to hydrogen peroxide (calculated by pure hydrogen peroxide) is 3:1, feeding into a fixed bed catalytic reactor (wherein the catalyst is a titanium-silicon molecular sieve TS-1 with the particle size of 3 mm), and the feeding airspeed is 1h calculated by hydrogen peroxide-1Meanwhile, surfactant (span-60 and tween-80 loaded on the carrier, span-60 pure substance amount is 0.01%, and tween-80 pure substance amount is 0.01%) accounting for 0.05% of the total amount of methanol, hydrogen peroxide and chloropropene is also fed into the fixed bed catalytic reactor, and chloropropene and hydrogen peroxide are reacted in the fixed bed catalytic reactor.
Introducing products generated in the fixed bed catalytic reactor, including epoxy chloropropane, a solvent, residual chloropropene and residual hydrogen peroxide, into a separator for separation, extracting the separated epoxy chloropropane and residual chloropropene, and further processing to obtain epoxy chloropropane; and introducing the separated solvent and residual hydrogen peroxide into a reactor filled with a catalyst, and introducing chloropropene simultaneously so as to continuously perform catalytic epoxidation reaction in the reactor.
And detecting, wherein the product generated by the reactor comprises epichlorohydrin, chloropropene, a solvent and water, and does not contain hydrogen peroxide, and the epichlorohydrin product is obtained after treatment.
Compared with the traditional chlorohydrin method, the method provided by the embodiment of the invention has the advantages of high efficiency, low energy consumption, low toxicity, low byproduct and no pollution.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A process for the preparation of epichlorohydrin comprising:
chloropropene is used as a raw material, hydrogen peroxide is used as an oxidant, a solvent and a surfactant are added, and the reaction is carried out in a fixed bed catalytic reactor.
2. The method of claim 1, wherein the molar ratio of the chloropropene to the hydrogen peroxide is 10:1-1:1, preferably 3:1-1.5:1, calculated as pure hydrogen peroxide.
3. The method according to claim 1 or 2, characterized in that the surfactant is a non-ionic surfactant, preferably a combination of span-ben and tween.
4. A method according to any one of claims 1 to 3, characterized in that the hydrogen peroxide solution is an aqueous solution with a concentration of 5% to 90%, preferably an aqueous solution with a concentration of 30% to 70%.
5. The method of any one of claims 1 to 4, wherein the catalyst in the fixed-bed catalytic reactor is a titanium silicalite with a particle size of 0.1mm to 10 cm.
6. A process according to any one of claims 1 to 5, characterized in that the solvent is methanol, ethanol, acetone, butanone or acetonitrile, preferably methanol.
7. The method according to any one of claims 1-6, further comprising:
and separating the product of the fixed bed catalytic reactor, introducing the separated solvent and residual hydrogen peroxide into another reactor, and simultaneously introducing chloropropene for reaction.
8. The method of claim 7, wherein the separation is by centrifugation or by standing.
9. The process of claim 7, wherein the further reactor is a fixed bed, an ebullated bed, a slurry bed or a fluidized bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010479299.9A CN111574481A (en) | 2020-05-29 | 2020-05-29 | Method for preparing epichlorohydrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010479299.9A CN111574481A (en) | 2020-05-29 | 2020-05-29 | Method for preparing epichlorohydrin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111574481A true CN111574481A (en) | 2020-08-25 |
Family
ID=72114276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010479299.9A Pending CN111574481A (en) | 2020-05-29 | 2020-05-29 | Method for preparing epichlorohydrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111574481A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172970A (en) * | 2007-10-12 | 2008-05-07 | 华东师范大学 | Method for producing epoxychloropropane |
| CN101434586A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Propylene chloride epoxidation process in the presence of hydrogen and oxygen |
| CN101481364A (en) * | 2009-02-24 | 2009-07-15 | 江苏扬农化工集团有限公司 | Continuous production method of epoxy chloropropane by hydrogen peroxide process |
| JP2011515350A (en) * | 2008-03-17 | 2011-05-19 | ヘキソン・スペシヤルテイ・ケミカルズ・ゲー・エム・ベー・ハー | Method for producing epichlorohydrin |
| CN102442978A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Alkene epoxidation method |
| CN110698435A (en) * | 2019-11-15 | 2020-01-17 | 广州大有精细化工厂 | Preparation method of epichlorohydrin |
-
2020
- 2020-05-29 CN CN202010479299.9A patent/CN111574481A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172970A (en) * | 2007-10-12 | 2008-05-07 | 华东师范大学 | Method for producing epoxychloropropane |
| CN101434586A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Propylene chloride epoxidation process in the presence of hydrogen and oxygen |
| JP2011515350A (en) * | 2008-03-17 | 2011-05-19 | ヘキソン・スペシヤルテイ・ケミカルズ・ゲー・エム・ベー・ハー | Method for producing epichlorohydrin |
| CN101481364A (en) * | 2009-02-24 | 2009-07-15 | 江苏扬农化工集团有限公司 | Continuous production method of epoxy chloropropane by hydrogen peroxide process |
| CN102442978A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Alkene epoxidation method |
| CN110698435A (en) * | 2019-11-15 | 2020-01-17 | 广州大有精细化工厂 | Preparation method of epichlorohydrin |
Non-Patent Citations (1)
| Title |
|---|
| 蔡丽蓉等: "低成本TS-1的制备及其在丙烯环氧化中的应用", 《工业催化》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1167695C (en) | Reacting of organic compound and hydroperoxide | |
| EP2462129B1 (en) | Process for producing an oxirane | |
| JP2008542371A (en) | Direct epoxidation method | |
| EP2462130B1 (en) | Process for producing propylene oxide | |
| CN101279958A (en) | Method for preparing epoxy chloropropane by epoxidation of propylene chloride | |
| TWI523689B (en) | Process for producing propylene oxide using a pretreated epoxidation catalyst | |
| JP5047444B2 (en) | Epoxide integrated manufacturing method | |
| US6838571B2 (en) | Oxirane production using peroxidized compound | |
| TWI485143B (en) | Epoxidation of an olefin | |
| US8927744B2 (en) | Process and system for producing an oxirane | |
| TWI466875B (en) | Method for making epoxides | |
| CN111574481A (en) | Method for preparing epichlorohydrin | |
| CN111606871B (en) | Preparation method of epichlorohydrin | |
| CN110357835A (en) | A kind of preparation method of epichlorohydrin | |
| EP2602251B1 (en) | Method for producing epoxy compound by oxidation | |
| US9051287B2 (en) | Method for producing epoxide | |
| CN105524028B (en) | A kind of chloropropene method for oxidation | |
| EP2501688B1 (en) | Epoxidizing of propylene | |
| CN107473940B (en) | Preparation method of dichloropropanol | |
| CN112174913A (en) | Reinforcing system and process for preparing 1,2-epoxy cyclopentane | |
| KR101662355B1 (en) | Epoxidation process | |
| JP2004269379A (en) | Method for producing propylene oxide | |
| CN106146430B (en) | Method that is a kind of while producing propylene oxide and acetone | |
| CN107954834A (en) | A kind of method for preparing dichlorohydrin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |