CN111574481A - A kind of method for preparing epichlorohydrin - Google Patents
A kind of method for preparing epichlorohydrin Download PDFInfo
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- 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
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010936 titanium Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
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- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
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- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 5
- 229920000053 polysorbate 80 Polymers 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000002808 molecular sieve Substances 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
- 239000000126 substance Substances 0.000 description 4
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- PVYDNJADTSAQQU-UHFFFAOYSA-N prop-1-ene;hydrochloride Chemical compound Cl.CC=C PVYDNJADTSAQQU-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 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 2
- -1 TS-1 Chemical compound 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 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
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007127 saponification reaction Methods 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
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-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
- 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
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- 125000004429 atom Chemical group 0.000 description 1
- 229960003237 betaine Drugs 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
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 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
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- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 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
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
本发明提供一种制备环氧氯丙烷的方法，所述方法包括：以氯丙烯为原料，双氧水为氧化剂，加入溶剂和表面活性剂，在固定床催化反应器中进行反应。本发明提供的方法通过催化作用以及溶剂和表面活性剂的促进作用，使双氧水与氯丙烯在固定床催化反应器中一步反应制得环氧氯丙烷，且催化剂易于分离，可以实现环氧氯丙烷高效率、低能耗、低毒、低副产物、无污染的绿色安全生产，完全可以替代传统氯醇法生产环氧氯丙烷。
The invention provides a method for preparing epichlorohydrin, which comprises the following steps: using chloropropene as a raw material, hydrogen peroxide as an oxidant, adding a solvent and a surfactant, and performing the reaction in a fixed-bed catalytic reactor. The method provided by the invention makes epichlorohydrin prepared by one-step reaction of hydrogen peroxide and allyl chloride in a fixed-bed catalytic reactor through catalysis and the promotion of solvents and surfactants, and the catalyst is easy to separate, so that epichlorohydrin can be realized. Green and safe production with high efficiency, low energy consumption, low toxicity, low by-products, and no pollution can completely replace the traditional chlorohydrin method to produce epichlorohydrin.
Description
技术领域technical field
本发明涉及有机化工中间体制备领域，更具体地，涉及一种制备环氧氯丙烷的方法。The invention relates to the field of preparation of organic chemical intermediates, and more particularly, to a method for preparing epichlorohydrin.
背景技术Background technique
环氧氯丙烷是一种重要的有机化工中间体，主要用于生产环氧树脂。目前，工业上制备环氧氯丙烷主要采用氯醇法，以氯丙烯、氯气和水经过氯醇化反应制备二氯丙醇，再进一步皂化得到环氧氯丙烷。在氯醇化反应中，以氯气作为氧化剂和氯源，水提供羟基，反应机理为氯气与水反应生成的次氯酸氧化氯丙烯的双键，双键上的电子转移给氯原子的同时氯原子与双键加成，随后羟基亲核进攻双键另一个碳原子加成生成二氯丙醇。Epichlorohydrin is an important organic chemical intermediate, mainly used in the production of epoxy resins. At present, the industrial preparation of epichlorohydrin mainly adopts the chlorohydrin method. Dichlorohydrin is prepared from allyl chloride, chlorine gas and water through chlorohydrin reaction, and then further saponification is used to obtain epichlorohydrin. In the chlorohydrin reaction, chlorine gas is used as the oxidant and chlorine source, and water provides hydroxyl groups. The reaction mechanism is that hypochlorous acid generated by the reaction of chlorine gas and water oxidizes the double bond of chloropropene, and the electrons on the double bond are transferred to the chlorine atom at the same time as the chlorine atom. Addition to the double bond followed by nucleophilic attack of the hydroxyl group on another carbon atom of the double bond generates dichloropropanol.
但是，氯醇法以剧毒的氯气为原料，安全性低；氧化副产物盐酸会导致氯醇化反应的原子利用率低，使得环氧氯丙烷得率低；氯气化学性质活泼，很容易发生副反应，产生副产物较多；与氯丙烯直接加成反应会生成低价值的三氯丙烷，为了控制目标产物浓度，需要加入大量的水稀释反应体系中氯气浓度，这不仅使得皂化分离过程能耗高，而且每吨环氧氯丙烷约产生难处理废水废渣，污染环境。However, the chlorohydrin method uses highly toxic chlorine gas as the raw material, which has low safety; the oxidation by-product hydrochloric acid will lead to low atom utilization in the chlorohydrin reaction, resulting in a low yield of epichlorohydrin; chlorine gas is chemically active and prone to side effects. The reaction produces many by-products; the direct addition reaction with allyl chloride will generate low-value trichloropropane, in order to control the concentration of the target product, it is necessary to add a large amount of water to dilute the chlorine concentration in the reaction system, which not only makes the saponification separation process energy consumption High, and about every ton of epichlorohydrin produces refractory waste water and slag, polluting the environment.
发明内容SUMMARY OF THE INVENTION
本发明实施例提供一种制备环氧氯丙烷的方法，通过催化作用以及溶剂和表面活性剂的促进作用，使双氧水与氯丙烯一步反应制得环氧氯丙烷，达到绿色、高效、节能的效果。The embodiment of the present invention provides a method for preparing epichlorohydrin. Through catalysis and the promotion of solvents and surfactants, hydrogen peroxide and chloropropene are reacted in one step to prepare epichlorohydrin, and the effects of green, high efficiency and energy saving are achieved. .
本发明实施例提供一种制备环氧氯丙烷的方法，包括：The embodiment of the present invention provides a method for preparing epichlorohydrin, comprising:
以氯丙烯为原料，双氧水为氧化剂，加入溶剂和表面活性剂，在固定床催化反应器中进行反应。Using chloropropene as raw material, hydrogen peroxide as oxidant, adding solvent and surfactant, the reaction is carried out in a fixed bed catalytic reactor.
相较于现有技术，本发明的有益效果：Compared with the prior art, the beneficial effects of the present invention:
本发明提供的方法可以实现环氧氯丙烷高效率、低能耗、低毒、低副产物、无污染的绿色安全生产，完全可以替代传统氯醇法生产环氧氯丙烷。The method provided by the invention can realize the green and safe production of epichlorohydrin with high efficiency, low energy consumption, low toxicity, low by-products and no pollution, and can completely replace the traditional chlorohydrin method to produce epichlorohydrin.
附图说明Description of drawings
图1为本发明实施例提供的制备环氧氯丙烷的工艺流程示意图，Fig. 1 is the process flow schematic diagram of preparing epichlorohydrin provided by the embodiment of the present invention,
图中，1：固定床催化反应器；2：分离器；3：反应器；4：表面活性剂；5：溶剂、双氧水和氯丙烯；6：第一产物；7：环氧氯丙烷和残余氯丙烯；8：溶剂和残余双氧水；9：氯丙烯；10：第二产物。In the figure, 1: fixed bed catalytic reactor; 2: separator; 3: reactor; 4: surfactant; 5: solvent, hydrogen peroxide and propylene chloride; 6: first product; 7: epichlorohydrin and residual Allyl chloride; 8: solvent and residual hydrogen peroxide; 9: allyl chloride; 10: second product.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention. If no specific technique or condition is indicated in the examples, the technique or condition described in the literature in the field or the product specification is used. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased through regular channels.
本发明实施例提供一种制备环氧氯丙烷的方法，包括：The embodiment of the present invention provides a method for preparing epichlorohydrin, comprising:
以氯丙烯为原料，双氧水为氧化剂，加入溶剂和表面活性剂，在固定床催化反应器中进行反应。Using chloropropene as raw material, hydrogen peroxide as oxidant, adding solvent and surfactant, the reaction is carried out in a fixed bed catalytic reactor.
反应可在常压或高压下进行。The reaction can be carried out under normal pressure or high pressure.
其中，所述溶剂可以是醇、酮、酸、酯或腈类，优选甲醇、乙醇、丙酮、丁酮或乙腈等常用试剂，进一步优选为甲醇。氯丙烯和双氧水不互溶，溶剂可以有效增加氯丙烯和双氧水的溶解度。溶剂的量为以充满反应床层为准。Wherein, the solvent can be alcohol, ketone, acid, ester or nitrile, preferably methanol, ethanol, acetone, methyl ethyl ketone or acetonitrile and other common reagents, more preferably methanol. Propylene chloride and hydrogen peroxide are immiscible, and the solvent can effectively increase the solubility of chloropropene and hydrogen peroxide. The amount of solvent is based on filling the reaction bed.
所述表面活性剂可为阴离子表面活性剂(如硬脂酸、十二烷基苯磺酸钠)、阳离子表面活性剂(如季铵化物)、两性离子表面活性剂(如卵磷脂、氨基酸型、甜菜碱型)、非离子表面活性剂(如脂肪酸甘油酯、脂肪酸山梨坦(司苯)、聚山梨酯(吐温))中的一种或多种。表面活性剂的加入可以进一步增大氯丙烯和双氧水的溶解度，提高反应转化率；也会加快反应物在催化剂表面的吸附和扩散速度，增加反应效率，延长催化剂的寿命。The surfactants can be anionic surfactants (such as stearic acid, sodium dodecylbenzenesulfonate), cationic surfactants (such as quaternary ammonium compounds), zwitterionic surfactants (such as lecithin, amino acid type) , betaine type), non-ionic surfactant (such as fatty acid glyceride, fatty acid sorbitan (span), polysorbate (Tween)) in one or more. The addition of surfactant can further increase the solubility of propylene chloride and hydrogen peroxide, improve the reaction conversion rate; it will also speed up the adsorption and diffusion of reactants on the surface of the catalyst, increase the reaction efficiency, and prolong the life of the catalyst.
优选地，所述表面活性剂为非离子表面活性剂，进一步优选为司苯和吐温的组合物，例如：司苯-60(加入量0.005％-0.5％)与吐温-80(加入量0.005％-0.5％)组合，或者司苯-80(加入量0.005％-0.5％)与吐温-60(加入量0.005％-0.5％)组合，或者司苯-60(加入量0.005％-0.5％)与吐温-60(加入量0.005％-0.5％)组合，或者司苯-80(加入量0.005％-0.5％)与吐温-80(加入量0.005％-0.5％)组合，等等。Preferably, the surfactant is a nonionic surfactant, more preferably a combination of sparge and Tween, for example: spar-60 (addition amount 0.005%-0.5%) and Tween-80 (addition amount 0.005%-0.5%) combination, or sparge-80 (addition amount 0.005%-0.5%) and Tween-60 (addition amount 0.005%-0.5%), or sparge-60 (addition amount 0.005%-0.5%) %) in combination with Tween-60 (addition 0.005%-0.5%), or stilbene-80 (addition 0.005%-0.5%) and Tween-80 (addition 0.005%-0.5%), etc. .
在本发明的优选实施方式中，先将司苯和吐温负载在一定量的载体上，然后再将包含载体的表面活性剂加入到反应体系中。其中，司苯占表面活性剂和载体总量的0.005wt％-0.5wt％，吐温占表面活性剂和载体总量的0.005wt％-0.5wt％。所述包含载体的表面活性剂占反应体系的质量百分比为0.0005％-0.1％，优选为0.005％-0.05％。所述反应体系指氯丙烯、双氧水和溶剂的总和。In a preferred embodiment of the present invention, sparene and tween are loaded on a certain amount of carrier first, and then the surfactant containing the carrier is added to the reaction system. Wherein, sparene accounts for 0.005wt%-0.5wt% of the total amount of the surfactant and the carrier, and Tween accounts for 0.005wt%-0.5wt% of the total amount of the surfactant and the carrier. The mass percentage of the surfactant including the carrier in the reaction system is 0.0005%-0.1%, preferably 0.005%-0.05%. The reaction system refers to the sum of allyl chloride, hydrogen peroxide and solvent.
所述双氧水(过氧化氢)可以是纯品，但从安全和经济角度考虑，优选使用浓度5％-90％的水溶液，进一步优选30％-70％的水溶液。The hydrogen peroxide (hydrogen peroxide) can be pure, but from the viewpoint of safety and economy, it is preferable to use an aqueous solution with a concentration of 5%-90%, more preferably an aqueous solution of 30%-70%.
所述氯丙烯与所述双氧水(以纯双氧水计)的摩尔比为10:1-1:1，优选为3:1-1.5:1。The molar ratio of the allyl chloride to the hydrogen peroxide (calculated in pure hydrogen peroxide) is 10:1-1:1, preferably 3:1-1.5:1.
所述固定床催化反应器中的催化剂采用钛硅分子筛，是指钛原子取代晶格骨架中部分硅原子的一类沸石总称。这类物质是现有技术中已知的，如具有类似ZSM-5硅酸铝沸石的MFI拓扑结构的含钛沸石即TS-1，具有类似ZSM-11硅酸铝沸石的MEL拓扑结构的含钛沸石即TS-2，以及具有与丝光沸石、ZSM-12、MCM-41、MCM-48和MWW同晶骨架结构的含钛分子筛等。以上钛硅分子筛可以商购也可自制。催化剂的颗粒粒径为0.1mm-10cm，优选为1mm-3mm。The catalyst in the fixed-bed catalytic reactor adopts titanium-silicon molecular sieve, which is a general term for a class of zeolites in which titanium atoms replace part of silicon atoms in the lattice framework. Such materials are known in the art, such as the titanium-containing zeolite having an MFI topology similar to the ZSM-5 aluminosilicate zeolite, namely TS-1, and the titanium-containing zeolite having a MEL topology similar to the ZSM-11 aluminosilicate zeolite. Titanium zeolite, namely TS-2, and titanium-containing molecular sieves with isomorphous framework structures with mordenite, ZSM-12, MCM-41, MCM-48 and MWW, etc. The above titanium-silicon molecular sieves can be commercially purchased or homemade. The particle size of the catalyst is 0.1 mm-10 cm, preferably 1 mm-3 mm.
进料时，优选将溶剂、双氧水和氯丙烯先混合，在反应器进料口处再与表面活性剂进行混合。进料可采用反应器上部或下部顺流进料。进料空速为以双氧水计为0.05-4h-1，优选为0.1-2h-1。When feeding, preferably the solvent, hydrogen peroxide and allyl chloride are mixed first, and then mixed with the surfactant at the feed port of the reactor. The feed can be co-current feed from the upper or lower part of the reactor. The feed space velocity is 0.05-4 h -1 in terms of hydrogen peroxide, preferably 0.1-2 h -1 .
基于上述实施例，本发明实施例提供的制备环氧氯丙烷的方法还包括：Based on the above-mentioned embodiment, the method for preparing epichlorohydrin provided in the embodiment of the present invention also includes:
将所述固定床催化反应器的产物进行分离，将分离后的溶剂和残余双氧水通入另一个反应器，同时通入氯丙烯进行反应。The product of the fixed-bed catalytic reactor is separated, and the separated solvent and residual hydrogen peroxide are passed into another reactor, and propene chloride is passed into the reaction at the same time.
具体可参见图1，将溶剂、双氧水和氯丙烯5以及表面活性剂4进料至固定床催化反应器1，在固定床催化反应器1内，氯丙烯和双氧水发生环氧化反应，生成的第一产物6包括环氧氯丙烷、溶剂、残余氯丙烯和残余双氧水。将第一产物6通入分离器2中进行分离，分离后的环氧氯丙烷和残余氯丙烯7采出，进一步处理后得到环氧氯丙烷；分离后的溶剂和残余双氧水8通入装有催化剂的反应器3，同时通入氯丙烯9，使得在反应器3内继续进行催化环氧化反应，生成的第二产物10包括环氧氯丙烷、氯丙烯、溶剂和水，经过处理后得到环氧氯丙烷产品。1 , the solvent, hydrogen peroxide,
其中分离器2可采用离心分离或静置分离。The
反应物在反应器中很难实现完全反应，当双氧水过量时残留物很多，故一般采取氯丙烯过量，但氯丙烯过量时也会残余少量双氧水，残余双氧水在后续分离时会分解产生氧气，增加工艺的危险性。本发明实施例中，固定床催化反应器1中双氧水只能反应90％～95％，会残余5％～10％的双氧水。本发明实施例将溶剂和残余双氧水8加入氯丙烯9，在反应器3中进一步催化反应后，可以使残余双氧水反应完全，即第二产物10中不含有双氧水，避免了残余双氧水分解产生氧气的不安全因素。The reactants are difficult to achieve complete reaction in the reactor. When the hydrogen peroxide is excessive, there are a lot of residues. Therefore, an excess of chloropropene is generally used. However, when the chloropropene is excessive, a small amount of hydrogen peroxide will remain. The residual hydrogen peroxide will be decomposed during subsequent separation to generate oxygen, increasing the Hazards of the craft. In the embodiment of the present invention, the hydrogen peroxide in the fixed bed
本发明实施例反应器3中之所以能使双氧水完全反应的原因是：固定床催化反应器1出口的第一产物6中仅剩5～10％的残余双氧水，双氧水的绝对含量较低，因此反应器3中氯丙烯与双氧水的摩尔比可达到较大值，有利于反应完全，而实际氯丙烯绝对量不大。当然也可同时采取降低空速和提高反应温度来使双氧水反应完全。甚至还可不使用固定床反应器，选用沸腾床、淤浆床或流化床等其它反应形式，来提高双氧水转化率，实现使残余5-10％的双氧水完全反应。The reason why the hydrogen peroxide can be completely reacted in the
实施例1Example 1
本发明实施例提供一种制备环氧氯丙烷的方法，具体如下：The embodiment of the present invention provides a kind of method for preparing epichlorohydrin, specifically as follows:
将甲醇、30％的双氧水和氯丙烯混合，氯丙烯与双氧水(以纯双氧水计)的摩尔比为3:1，进料至固定床催化反应器(其中催化剂为粒径3mm的钛硅分子筛TS-1)，进料空速为以双氧水计为1h-1，同时将占甲醇、双氧水和氯丙烯总和0.05％的表面活性剂(负载在载体上的司苯-60与吐温-80，司苯-60纯物质量为0.01％，吐温-80纯物质量为0.01％)也进料至固定床催化反应器，氯丙烯和双氧水在固定床催化反应器中进行反应。Methanol, 30% hydrogen peroxide and chloropropene were mixed, the molar ratio of chloropropene and hydrogen peroxide (calculated in pure hydrogen peroxide) was 3:1, and fed to a fixed bed catalytic reactor (wherein the catalyst was a titanium silicon molecular sieve TS- 1), the feed space velocity is 1h -1 in terms of hydrogen peroxide, and the surfactant (span-60 and Tween-80 loaded on the carrier, span-60 and Tween-80 that are loaded on the carrier simultaneously will account for 0.05% of the total of methanol, hydrogen peroxide and allyl chloride. -60 pure substance is 0.01%, Tween-80 pure substance is 0.01%) is also fed to the fixed bed catalytic reactor, and the reaction of propene chloride and hydrogen peroxide is carried out in the fixed bed catalytic reactor.
固定床催化反应器中生成的产物包括环氧氯丙烷、溶剂、残余氯丙烯和残余双氧水，将其通入分离器中进行分离，分离后的环氧氯丙烷和残余氯丙烯采出，进一步处理后得到环氧氯丙烷；分离后的溶剂和残余双氧水通入装有催化剂的反应器，同时通入氯丙烯，使得在反应器内继续进行催化环氧化反应。The products generated in the fixed bed catalytic reactor include epichlorohydrin, solvent, residual chloropropene and residual hydrogen peroxide, which are passed into the separator for separation, and the separated epichlorohydrin and residual chloropropene are extracted for further processing Then, epichlorohydrin is obtained; the separated solvent and residual hydrogen peroxide are passed into a reactor equipped with a catalyst, and at the same time, propene chloride is passed into the reactor, so that the catalytic epoxidation reaction is continued in the reactor.
经检测，反应器生成的产物包括环氧氯丙烷、氯丙烯、溶剂和水，不包含双氧水，经过处理后得到环氧氯丙烷产品。After testing, the product generated by the reactor includes epichlorohydrin, chloropropene, solvent and water, but does not contain hydrogen peroxide, and the epichlorohydrin product is obtained after treatment.
本发明实施例的方法相比传统氯醇法更高效、低能耗、低毒、低副产物、无污染。Compared with the traditional chlorohydrin method, the method of the embodiment of the present invention is more efficient, low in energy consumption, low in toxicity, low in by-products, and pollution-free.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail above with general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention fall within the scope of the claimed protection of the present invention.
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