CN102311408B - Method for preparing styrene oxide by waste water zero discharge process - Google Patents

Method for preparing styrene oxide by waste water zero discharge process Download PDF

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CN102311408B
CN102311408B CN201010213560.7A CN201010213560A CN102311408B CN 102311408 B CN102311408 B CN 102311408B CN 201010213560 A CN201010213560 A CN 201010213560A CN 102311408 B CN102311408 B CN 102311408B
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reaction
styrene oxide
method
bromide
styrene
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CN102311408A (en
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张宾山
白瑞刚
刘文革
李文祥
张连海
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山东瀛洋香精香料有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/24Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
    • C07D301/26Y being hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring heteroatom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/04Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Abstract

废水零排放工艺制备环氧苯乙烷的方法,本发明涉及化工材料中间体领域,具体地说是一种由苯乙烯制备环氧苯乙烷的工艺。 The method of preparation of zero discharge of wastewater styrene oxide, the present invention relates to the field of chemical intermediates materials, in particular prepared from a styrene-styrene oxide process. 本发明使用代替氯酸钠的氧化剂,选择经改进的溴醇法氧化苯乙烯,以废水零排放工艺制备环氧苯乙烷。 The present invention, using an oxidizing agent in place of sodium chlorate and choose improved method epibromohydrin, styrene oxide, zero discharge of process wastewater to be prepared styrene oxide. 该方法的特点是:1,使用代替氯酸钠的氧化剂进行溴醇化反应,氧化副产物便于处理,没有污染。 Characteristics of the method are: 1, using an oxidizing agent in place of sodium chlorate were alcoholate bromine reaction, oxidation by-products to facilitate handling, no pollution. 2,溴醇化废水处理采用降温或浓缩等方法,使反应生成的盐析出,消除了污染。 2, using the wastewater treatment bromo alkoxides cooling or concentration method, etc., the salt precipitate produced by the reaction, to eliminate the contamination. 3,盐析出时,若反应体系中存在多余的水,可以通过盐本身析出时携带结晶水的形式移出反应体系。 3, a salt precipitated in the reaction system if excess water is present, carrying out the reaction in the form of water of crystallization when the system can be precipitated by the salt itself. 析出盐之后的母液继续用来配制硫酸等溶液,继续参与反应,皂化废水添加溴盐循环套用,使得该工艺无任何污水排放,真正做到污水零排放。 The mother liquor after precipitation of salts such as sulfuric acid solution used for the preparation continued, continue to participate in the reaction, saponification wastewater circulation apply bromine salt, so that the process has no sewage, sewage truly zero emissions.

Description

废水零排放工艺制备环氧苯乙烷的方法 Waste Water process for preparing styrene oxide emissions process

技术领域 FIELD

[0001] 本发明涉及化工材料中间体领域,具体地说是一种由苯乙烯制备环氧苯乙烷的工 [0001] The present invention relates to the field of chemical materials, intermediates, in particular to a production of ethylene oxide from styrene benzene ENGINEERING

-H- -H-

O O

背景技术 Background technique

[0002] 环氧苯乙烷又称氧化苯乙烯,是重要的有机中间体,可用作环氧树脂稀释剂、紫外吸收剂、增香剂,也是有机合成、制药、香料工业的重要中间体,如:环氧苯乙烷是生产左旋咪唑的原料;另外环氧苯乙烷催化加氢制得的苯乙醇是玫瑰油、丁香油、橙花油的主要成分,并且广泛用于配制食品、烟草、肥皂及化妆品香精,是一种香气好、价格便宜、用量非常大的重要合成香料,其用量每年以万吨计,而我国是世界上苯乙醇的主要生产国,占据世界80%的市场份额。 [0002] styrene oxide, styrene oxide, also known, is an important intermediate, useful as an important intermediate of an epoxy resin diluent, an ultraviolet absorber, flavoring agents, organic synthesis, pharmaceutical, perfume industry , such as: styrene oxide raw material is levamisole; additionally styrene oxide by catalytic hydrogenation of phenylethyl alcohol is the main component of rose oil, clove oil, neroli oil, and is widely used in food preparation, tobacco, soap and cosmetics and fragrance, a scent is good, cheap, very large amount of important synthetic perfumes, the amount of tons per year, while China is the world's leading producer of ethanol, benzene, accounting for 80% of the world market share. 因此,环氧苯乙烷的工业生产在香料工业等相关领域至关重要。 Accordingly, industrial production of styrene oxide is essential in the relevant field of perfumery industry.

[0003]目前,工业上生产环氧苯乙烷主要采用卤醇法。 [0003] At present, industrial production of styrene oxide mainly halohydrin method. 卤醇法氯酸钠工艺是我国在二十世纪八十年代开发成功的工艺,由于该工艺技术难度小、操作简单、成本低、质量好,很快取代了其他生产工艺,并逐步成为世界主流生产工艺。 Halogen alcohol law chlorite process is the successful development of our country in the 1980s technology, the technology difficulty due to the small, simple, low cost, good quality, and soon replaced the other production process, and gradually become the mainstream of the world Production Process. 这个工艺的关键步骤是第一步的溴醇化工序:苯乙烯悬浮在水溶液中,搅拌下同时滴加硫酸溶液、溴化钠溶液、氯酸钠溶液,反应完成后静置分层,有机相为溴醇,水相为废水。 The key step is the first step of the process bromo alkoxides steps of: styrene was suspended in an aqueous solution, sulfuric acid solution was added dropwise while stirring, sodium bromide, sodium chlorite, allowed to stand after the completion of the reaction, and the organic phase was epibromohydrin, the aqueous phase of the waste water. 溴醇经皂化后得到环氧苯乙烷,废水排放。 Bromohydrin obtained after saponification styrene oxide, wastewater. 反应路线如图1,工艺流程如图2。 Scheme 1, the process shown in Figure 2.

[0004] 但该法污染严重,会产生大量氧化性、高盐、强酸性废水,难于治理,因而带来严重的环境压力。 [0004] However, the method pollution, will produce a large oxidation resistance, high salt and strong acid waste water, treatment is difficult, and thus serious environmental pressure. 在环境保护要求不断提高的今天,该生产路线必将很快被淘汰。 In the continuous improvement of environmental protection requirements of today, the production line will soon be eliminated. 因此,研宄开发清洁经济的绿色合成技术迫在眉睫。 Therefore, the study based on the economic development of clean green synthesis technology is imminent.

[0005] 近年来,人们主要从氧源、催化剂方面研宄环氧化苯乙烯过程,寻找合适的、可以替代氯酸钠等的新型氧化剂。 [0005] In recent years, mainly from an oxygen source, a Subsidiary aspects catalyst epoxidized styrene process, to find a suitable, novel chlorite can replace an oxidizing agent. 以过氧化氢、有机过氧化物如过氧乙酸等、亚碘酞苯以及氧气或空气作为环氧化反应的氧化剂在文献中已有大量报道。 Hydrogen peroxide, organic peroxides such as peracetic acid, ethylene-iodo-benzene, and phthalocyanine oxygen or air as an oxidizing agent of the epoxidation reaction have been numerous reports in the literature. 但过酸,如:过氧乙酸等,价格昂贵,且生产过程中易发生剧烈反应,存在安全隐患。 However, peracids, such as: peracetic acid, are expensive, and the production process prone to violent reaction, there are security risks. 亚碘酞苯来源有限、价格昂贵,难以用于工业化生产。 Phenylene alkylene phthalate limited sources of iodine, expensive, difficult to use for industrial production. 目前人们最关注的是用经济、环保的氧化剂如双氧水、氧气等来实现无污染的工业化生产。 There is now most concerned with economic, environmental oxidants such as hydrogen peroxide, oxygen, etc. to achieve pollution-free industrial production.

[0006] 中国专利CN101346362A公开了一种使用含钴沸石和氧气将苯乙烯催化环氧化成环氧苯乙烷的方法。 [0006] Chinese Patent CN101346362A discloses a zeolite containing cobalt and oxygen into the catalytic epoxidation of styrene to styrene oxide method. 该方法使用氧气在钴交换沸石催化下将苯乙烯环氧化成环氧苯乙烷。 The method of using oxygen in the cobalt-exchanged zeolites were epoxidized styrene styrene oxide. 并研宄了在钴交换沸石催化剂中,吸附的水分子以及碱金属和碱土金属阳离子助催化剂对于该反应转化率和选择性的影响。 And a Subsidiary of cobalt exchanged zeolite catalyst, the adsorbed water molecules and the effect of alkali and alkaline earth metal cationic promoters for this reaction conversion and selectivity. 该方法的优点是采用了非均相催化剂,后处理容易,较均相催化剂污染小。 The advantage of this method is the use of heterogeneous catalysts, easy post treatment, less pollution than the homogeneous catalyst. 但缺点是需要使用DMF,DMA,1,4- 二氧六环等溶剂,价格较高,回收耗能及损耗比较大,氧气参加反应,需要密闭或高压体系,设备要求高。 But the disadvantage is the need to use DMF, DMA, 1,4- solvent such as dioxane, higher prices, recovery and energy loss is relatively large, oxygen participate in the reaction, or a closed high pressure system requires high equipment requirements. 该方法的转化率和选择性也不是太理想,距离工业化还有一段距离。 Conversion and selectivity of the process would not be good, still some distance from industrialization.

[0007] 中国专利CN101434587A公开了一种催化氧化苯乙烯合成环氧苯乙烷的方法,该方法在一定温度和压力下,将苯乙烯、氧气、氢气、稀释气体、溶剂和催化剂进行混合接触反应,催化剂为一种部分或全部为空心结构的微孔钛硅材料或含有该微孔钛硅材料的组合物。 [0007] Chinese Patent CN101434587A discloses a process for catalytic synthesis of styrene oxide styrene oxide, which at a certain temperature and pressure, styrene, oxygen, hydrogen, diluent gas, solvent, and catalyst contact reaction mixture , as a part or all of the catalyst is titanium silicate material microporous hollow structure or a composition containing titanium silicalite the microporous material. 该方法的优点是使用固体催化剂,后处理容易,污染小,但缺点是催化剂制备非常繁琐,苯乙烯转化率非常低(< 20% ),难以工业化生产。 The advantage of this method is that using a solid catalyst, easy post treatment, little pollution, but the disadvantage is very cumbersome preparation of the catalyst, the conversion of styrene is very low (<20%), industrial production difficult.

[0008] 中国专利CN101463020A公开了一种直接对苯乙烯进行氧化合成环氧苯乙烷的方法。 [0008] Chinese Patent CN101463020A discloses a process for the direct oxidation of styrene to styrene oxide synthesis. 该方法将Ag-γ -ZrP作为催化剂,以叔丁基过氧化氢为氧源,乙腈为溶剂,在氮气气氛,70-90°C的反应条件下,由苯乙烯直接环氧化合成环氧苯乙烷。 The method as Ag-γ -ZrP catalyst, tert-butyl hydroperoxide as an oxygen source, acetonitrile as a solvent, under a nitrogen atmosphere, the reaction conditions of 70-90 ° C, by the direct epoxidation of styrene ethylene synthesis ethylbenzene. 苯乙烯转化率最高可达92 %,环氧苯乙烷选择性最高可达96 %。 The highest conversion rate of 92% styrene, styrene oxide selectivity of up to 96%. 该方法的转化率和选择性比较理想,但缺点是催化剂价格昂贵、不易制备,所用试剂成本较高,难以规模化工业生产。 Conversion and selectivity of the process is desirable, expensive catalyst is a disadvantage, easy preparation, high cost of reagents used, it is difficult to scale industrial production.

[0009] 中国专利CN1557554A和CN1557553A公开了一种以氧气为氧源的苯乙烯环氧化制环氧苯乙烷的固体催化剂。 [0009] Chinese patent CN1557554A and CN1557553A disclose a source of oxygen-oxygen styrene epoxidation of styrene oxide solid catalyst. 该催化剂组成为=HiAnVTM1, M11J0.Al2O3.XS12, [M1,M11]0.Al2O3.XS12S微孔分子筛的化学表不式,MS Mn分别为一价和二价金属,x为分子筛的硅铝比,An+为第VIII族金属离子m为第VIII族金属离子在催化剂中的重量百分含量。 The catalyst composition = HiAnVTM1, M11J0.Al2O3.XS12, [M1, M11] 0.Al2O3.XS12S table does not microporous molecular sieves chemical formula, MS Mn respectively, monovalent and divalent metal, x is an aluminosilicate zeolite ratio , An + is a group VIII metal ion and m is a group VIII metal ion in weight percent catalyst. 微孔分子筛为X,Y,L,Beta, Mordenite, MCM-22等或孔径为1.5〜30nm的介孔二氧化娃,第VIII族金属为铁或钴。 Microporous molecular sieve of X, Y, L, Beta, Mordenite, MCM-22 mesoporous pore diameter or the like baby 1.5~30nm dioxide, the Group VIII metal is iron or cobalt. 在合适的反应条件下苯乙烯的转化率在4小时之内达到40%以上,环氧化物的选择性在60%以上,且除少量的苯乙醛和苯甲酸外,其它副产物均为苯甲醛,催化剂在多次重复使用后苯乙烯的转化率和环氧化物的选择性无明显下降。 Conversion of styrene reached under suitable reaction conditions within 4 hours more than 40%, selectivity to epoxide in 60% or more, and in addition a small amount of acid and phenylacetaldehyde, other byproducts are benzene formaldehyde, after repeated use of the catalyst in the conversion and epoxide selectivity decreased without styrene. 该方法具有使用固体催化剂的优点,如污染小,易于处理等;但缺点是转化率和选择性比较低,产物分离等比较困难,成本提高。 This method has the advantage of using a solid catalyst, such as little pollution, easy handling and the like; but the drawback is a relatively low conversion rate and selectivity, product separation is difficult, the cost increase.

[0010] 美国专利US4894467公开了一种以氧气为氧源,以含银及钾、钠、锂等的氢氧化物为活性物质,负载于惰性无机固体载体上的催化剂催化,200-350°C气相反应得到环氧苯乙烷的方法。 [0010] U.S. Patent No. US4894467 discloses a source of oxygen is oxygen, containing silver and potassium hydroxides, sodium, lithium, etc. as an active material, Catalyst supported on an inert inorganic solid carrier, 200-350 ° C the method of gas-phase reaction of styrene oxide. 该方法因要在200-350°C气相反应,对设备及工艺控制要求比较高,不易实现工业化。 The method to be due to a gas phase reaction at 200-350 ° C, relatively high equipment and process control requirements, easy to industrialize.

[0011] 美国专利US6534661公开了一种以氧气为氧源,以含铂、钯等贵金属活性物质,负载于含钛的硅载体上的催化剂催化,200-350°C气相反应得到环氧化合物的方法。 [0011] U.S. Patent No. US6534661 discloses an oxygen gas as an oxygen source, platinum, palladium and other precious metal active material supported on a titanium-containing Catalyst silicon carrier, 200-350 ° C to give a gas phase reaction of an epoxy compound method. 该方法因要在200-350°C气相反应,且反应时间长,需要一定压力,对设备及工艺控制要求比较高,而且催化剂需要使用贵金属,制备繁琐,很难实现工业化生产。 The method to be due to a gas phase reaction at 200-350 ° C, and the reaction time is long, requires a certain pressure, the equipment and process control requirements are relatively high, and require the use of a noble metal catalyst, prepared cumbersome, difficult to realize industrial production.

[0012] 由此可见:使用分子氧做为氧化剂氧化苯乙烯制备环氧苯乙烷的研宄虽然是当前的一个研宄热点,但该路线目前还很不成熟,其缺点主要表现在: [0012] Thus: using molecular oxygen as the oxidant study based on the production of styrene oxide styrene oxide, although a study based on the current focus, but the route is currently still immature, mainly in its shortcomings:

[0013] 1,对催化剂要求很高,多数该类催化剂价格昂贵、制备工艺复杂; [0013] 1, demanding the catalyst, the majority of such catalysts are expensive, complicated preparation process;

[0014] 2,反应条件较苛刻,很多需要高温气相反应或高压反应,或使用价格较高、回收困难的溶剂或其他助剂; [0014] 2, the reaction conditions more stringent, many require high temperature or high pressure reaction vapor phase reaction, or the use of more expensive, difficult recovery of solvents or other additives;

[0015] 3,反应收率不高; [0015] 3, the reaction yield is not high;

[0016] 4,对工艺、设备要求高,不利于工业化生产。 [0016] 4, to high technology, equipment requirements, is not suitable for industrial production.

[0017] H2O2是另一种清洁的氧化剂,作为氧化剂,其唯一的副产物是水,反应条件温和,对环境友好,符合绿色化工工艺的标准。 [0017] H2O2 is another clean oxidant, as an oxidant, its only byproduct is water, mild reaction conditions, environmentally friendly, in line with standard green chemical processes. 但采用绿色氧化剂双氧水作为氧化剂时,由于苯乙烯及其氧化产物都不溶于水,反应体系为两相,不利于氧化反应的进行,采取向反应体系中加入大量的挥发性有机溶剂如丙酮、四氢呋喃、甲醇和乙睛等作为共溶剂的方法,这又与绿色化学的基本原则相违背。 But the use of environmentally friendly oxidant hydrogen peroxide as the oxidant, since oxidation product of styrene and not soluble in water, two-phase reaction system is not conducive to the oxidation reaction, to take a large amount of volatile organic solvent such as acetone is added to the reaction system, tetrahydrofuran , methanol, and acetonitrile, etc. as the method of co-solvent, which in turn contrary to the principles of green chemistry.

[0018] 迄今为止,一些以Mo,V和Ti为活性组分的催化剂用于H2O2氧化苯乙烯制备环氧苯乙烷和苯甲醛等工艺,取得了一定的进展。 [0018] To date, several to Mo, V and Ti as an active component of the catalyst H2O2 for preparing styrene oxide and styrene oxide benzaldehyde process, has made some progress. 图3为以双氧水为氧化剂制备环氧苯乙烷的反应路线图。 Figure 3 is a reaction scheme hydrogen peroxide in FIG preparing styrene oxide oxidant.

[0019] 早期探索得到的结果很差,比如:美国专利US3806467公开了一种以过氧化氢为氧源,以双(三甲锡氧基)钼酸为催化剂催化合成环氧苯乙烷的方法。 Results [0019] Exploration of earlier obtained is poor, for example: U.S. Patent No. US3806467 discloses a hydrogen peroxide as an oxygen source, bis (trimethyltin yloxy) synthesized acid to styrene oxide catalyst. 但该方法收率很低,只有3% (基于过氧化氢)。 However, this method yields very low, only 3% (based on hydrogen peroxide). 美国专利US3953362公开了一种以过氧化氢为氧源,以含氧的钼化合物为催化剂催化合成环氧化合物的方法。 U.S. Patent US3953362 discloses a hydrogen peroxide as the oxygen source, oxygen-containing molybdenum compound as catalyst synthesis of the epoxy compound. 但该方法对水敏感,要求过氧化氢的含水量小于1%,这在工业生产上是很难实施的。 However, this method is sensitive to water, the water content of the hydrogen peroxide had required less than 1%, which is very difficult in industrial production embodiment. 还有一些使用氟化醇做溶剂的方法(美国专利US4418203)或高压反应持续除水的办法(美国专利US4157346)都很难实现工业化生产。 There are also methods of using the fluorinated alcohol as solvent (U.S. Patent No. US4418203) or continuous high pressure reactor water removal approach (U.S. Patent No. US4157346) are difficult to be industrialized. 后来人们采用使用胺类助催化剂的办法来提高该类反应的效果(美国专利US5041569),但该方法无疑提高了反应处理的难度,增加成本。 Later, people take measures to use amine co-catalyst to enhance the effect of such reactions (US Patent US5041569), but which undoubtedly increased the difficulty of the reaction process, increasing costs.

[0020] 最近,美国专利US20050065355公开了一种以过氧化氢为氧源,以负载型纳米金为催化剂催化合成环氧化合物的方法。 [0020] Recently, U.S. Patent No. US20050065355 discloses a hydrogen peroxide as an oxygen source, a load of gold nano Catalytic synthesis of epoxy compound. 但该方法使用的催化剂昂贵且制备困难,距离工业化还很遥远。 However, the method used in the catalyst preparation is difficult and expensive, are far from industrialization.

发明内容 SUMMARY

[0021] 本发明的主要目的在于在现有技术基础上提供一种废水零排放生产环氧苯乙烷的清洁新工艺。 [0021] The main object of the present invention to provide a zero emission styrene oxide production process for a new waste water cleaning in the prior art basis.

[0022] 本发明提供一种废水零排放工艺制备环氧苯乙烷的方法,包括如下步骤: [0022] The present invention provides a method for the preparation of zero waste water discharge styrene oxide process, comprising the steps of:

[0023] I)苯乙烯在溴盐水溶液、酸和氧化剂存在下控温-15〜150°C进行溴醇化反应,反应结束后静置,得到废水一和油层一; [0023] I) an aqueous solution of styrene at temperature, acid bromide and the oxidant bromine alcoholate -15~150 ° C for reaction, after the reaction was allowed to stand to give an oil layer and a wastewater;

[0024] 2)油层一加入碱溶液进行皂化反应,反应毕,分出油层二,得到环氧苯乙烷粗品及废水二,粗品经精馏提纯得到环氧苯乙烷成品; [0024] 2) oil was added a solution of an alkali saponification reaction, the reaction was completed, the oil layer was separated two, styrene oxide to give the crude two and wastewater, crude product purified by distillation to give the finished styrene oxide;

[0025] 3)废水二主要含有溴盐,经添加部分溴盐调配浓度至5〜50%后继续用于第一步溴醇化反应;将废水一析出盐;析出固体后的废水再次用于配制溴醇化反应所用的溶液。 [0025] 3) two wastewater containing mainly bromide, the bromide salt was added after the formulation to a concentration of 5~50% portion continue the reaction for the first step-bromo alkoxides; the waste water to precipitate a salt; wastewater precipitated solid was again used in formulating the reaction solution used bromo alkoxides.

[0026] 步骤I)所述的氧化剂是满足下列条件的氧化剂中的一种或多种或它们的溶液:氧化产物为水或易于清除的盐或易于除去的有机物。 Said oxidant [0026] Step I) satisfies the following conditions an oxidizing agent or a solution thereof, or more: the oxidation product is easy to remove water or organic salts or easily removable.

[0027] 步骤I)所述的氧化剂可以是:过硫酸钠、过硫酸铵、过硫酸钾、过氧化钠、过氧化钾、过碳酸铵、过碳酸钠、过硼酸钠、过氧乙酸、过氧苯甲酸、过氧化二叔丁基、叔丁基过氧化氢,过氧化氢、氧气或臭氧的一种或多种,及含有上述物质或可以原位生成上述物质的试剂。 Oxidant [0027] Step I) may be said: sodium persulfate, ammonium persulfate, potassium persulfate, sodium peroxide, potassium peroxide, ammonium carbonate, sodium percarbonate, sodium perborate, peracetic acid, oxybenzoate, tert-butyl peroxide, t-butyl hydroperoxide, hydrogen peroxide, one kind or more of oxygen or ozone, and containing the substance or agent may be generated in situ above.

[0028] 步骤I)所述的氧化剂优选:过硫酸钠、过硫酸铵、过氧化氢、过碳酸钠、过碳酸铵、过硼酸钠、氧气、过氧化二叔丁基、叔丁基过氧化氢;必要时可加入助氧化剂;步骤I)所述的酸可以是硫酸、磷酸、硝酸、高氯酸或对甲苯磺酸。 [0028] Step I) The oxidizing agent is preferably: sodium persulfate, ammonium persulfate, hydrogen peroxide, sodium percarbonate, ammonium carbonate, sodium borate, oxygen, t-butyl peroxide, t-butyl peroxide hydrogen; pro-oxidant may be added if necessary; step I) the acid may be sulfuric acid, phosphoric acid, nitric acid, perchloric acid or p-toluenesulfonic acid.

[0029] 步骤I)所述的溴盐可以是溴化钠、溴化钾、溴化铵、溴化镁、溴化钙、其他碱金属的溴化物或其他碱土金属的溴化物中的一种或几种。 [0029] Step I) according to the bromide salt can be a sodium bromide, potassium bromide, ammonium bromide, magnesium bromide, calcium bromide bromide, an alkali metal bromide or other alkaline earth metal in the other or more.

[0030] 步骤I)所述的苯乙烯:溴盐:酸:氧化剂=I: 0.5〜5: 0.5〜5: 0.5〜10,摩尔比,其中酸若是多元酸则以实际发挥作用的氢离子的摩尔数计。 [0030] Step I) the styrene: bromide: acid: oxidizing agent = I: 0.5~5: 0.5~5: 0.5~10, molar ratio, wherein the acid polyacid places if the actual functioning of hydrogen ions the number of moles.

[0031] 步骤3)中的废水一采用降温、蒸发、反渗透或挥发浓缩的方法,使反应生成的盐析出。 Wastewater [0031] Step 3) using a cooling, evaporation, reverse osmosis or volatile method of concentrating, precipitated the salt produced by the reaction.

[0032] 步骤3)优选降温法使反应生成的盐析出。 [0032] Step 3) cooling method is preferably the salt precipitates formed by the reaction.

[0033] 步骤I)使用氧化剂时加入促进氧化效果的物质,如:铜、锰、铁、铬、镍和钒的盐。 When using an oxidizing agent is added [0033] Step I) effect the oxidation promoting substance, such as: copper salts, manganese, iron, chromium, nickel and vanadium.

[0034] 图4是本发明的反应路线图。 [0034] FIG. 4 is a reaction scheme of the present invention.

[0035] 本发明的有益效果是:以苯乙烯为原料,对传统溴醇法进行大胆改进,进而实现以废水零排放效果生产环氧苯乙烷的绿色新工艺: [0035] Advantageous effects of the present invention are: styrene as starting material, the traditional method epibromohydrin bold improvement, thus achieving the effect of zero discharge of waste water to produce styrene oxide green New Process:

[0036] 1,使用代替氯酸钠的氧化剂进行溴醇化反应,氧化副产物便于处理,没有污染。 [0036] 1, using in place of the oxidizing agent is sodium chlorate bromine alcoholate reaction, oxidation by-products to facilitate handling, no pollution.

[0037] 2,废水I处理采用降温或浓缩等方法,使反应生成的盐(例如硫酸钠以芒硝的形式)析出,消除了污染。 [0037] 2, I wastewater treatment using other cooling methods or concentration, the salt produced by the reaction (e.g., sulfate in the form of Glauber's salt) is precipitated, to eliminate contamination.

[0038] 3,盐析出时,若反应体系中存在多余的水,可以通过盐本身析出时携带结晶水的形式移出反应体系。 [0038] 3, a salt precipitated in the reaction system if excess water is present, carrying out the reaction in the form of water of crystallization when the system can be precipitated by the salt itself.

[0039] 4,析出盐之后的母液继续用来配制酸等溶液,继续参与反应,使得该工艺无任何污水排放,真正做到污水零排放。 [0039] 4, the mother liquor after the precipitation of the salt solution was used to prepare the acid continues to continue to participate in the reaction, such that the process has no sewage, sewage truly zero emissions.

附图说明 BRIEF DESCRIPTION

[0040] 图1卤醇法氯酸钠法工艺反应路线图 [0040] FIG. 1 process reactor epihalohydrin method chlorite method roadmap

[0041] 图2是氯酸钠法工艺流程图 [0041] FIG. 2 is a process flow diagram chlorite

[0042] 图3是以双氧水为氧化剂制备环氧苯乙烷的反应路线图 [0042] FIG. 3 is a hydrogen peroxide as an oxidizing agent prepared styrene oxide reaction scheme

[0043] 图4是本发明的反应路线图 [0043] FIG. 4 is a reaction scheme of the present invention, FIG.

[0044] 图5是实施例2的反应路线图 [0044] FIG. 5 is a reaction scheme of Example 2

[0045] 图6是实施例2的工艺流程图 [0045] FIG. 6 is a process flow diagram of the embodiment 2

具体实施方式 Detailed ways

[0046] 实施例1 [0046] Example 1

[0047] 配制50%硫酸溶液100千克,溴化钠溶液(含纯溴化钠103千克)350千克,30%液碱溶液134千克。 [0047] The formulated solution 100 kg 50% sulfuric acid, sodium bromide solution (containing 103 kg of pure sodium bromide) 350 kg, 134 kg of 30% caustic soda solution.

[0048] 将苯乙烯104千克一次性投入1000L搪瓷釜内,加入50克硫酸亚铁;开动搅拌,升温至75°C开始滴加120千克30%过氧化氢溶液、溴化钠溶液和硫酸溶液;三种物料在10小时内同时加完,滴加过程中温度控制在65〜80°C滴加完后,继续反应10小时,温度控制在75〜80°C,停搅拌,取样,检测合格即为反应终点,静置,分去油层,水层通冷降温至_15°C,析出芒硝晶体315千克,滤出固体,母液用于配制溴醇化所需的各种溶液。 [0048] 104 kg of styrene into the disposable 1000L enamel kettle, 50 grams of ferrous sulfate; Stirring was heated to 75 ° C the dropwise addition of 120 kg of 30% hydrogen peroxide solution, sulfuric acid solution and a solution of sodium bromide ; three materials simultaneously added over 10 hours, during the addition the temperature controlled at 65~80 ° C after the dropwise addition, the reaction was continued for 10 hours at controlled temperature 75~80 ° C, stop stirring, sampling, testing qualified is the end of the reaction, allowed to stand, points to the reservoir, the aqueous layer cooled through cooling to _15 ° C, 315 kg precipitated Glauber's salt crystals, the solid was filtered off, the mother liquor bromo alkoxides used in formulating the various solutions needed. 将溴代苯乙醇一次性投入皂化釜内;开搅拌,控温50°C,开始滴加液碱;8小时加完,然后继续反应8小时,温度控制在45〜55°C;反应结束后,静置半小时,检测合格即为反应终点;放出下层的回收溴化钠溶液,将料液放入成品罐内,溴化钠溶液经测试含量后添加新的溴化钠调配浓度至29.4%,继续用于溴醇化反应。 The disposable bromobenzene ethanol into the saponification reactor; open stirring, temperature 50 ° C, dropwise addition of caustic soda; 8 hours the addition was complete, then the reaction was continued for 8 hours at controlled temperature 45~55 ° C; after completion of the reaction , allowed to stand for half an hour, the reaction endpoint is the detection of qualified; lower discharge recovering sodium bromide solution, was put into the finished feed tank, the content of the test solution was added the sodium bromide sodium bromide new formulation to a concentration of 29.4% continue reaction for bromo alkoxides. 环氧苯乙烷收率75.7%。 Yield 75.7% styrene oxide.

[0049] 实施例2 [0049] Example 2

[0050] 配制50%硫酸溶液100千克,溴化钠溶液(含纯溴化钠103千克)360千克,30%液碱溶液134千克。 [0050] The formulated solution 100 kg 50% sulfuric acid, sodium bromide solution (containing 103 kg of pure sodium bromide) 360 kg, 134 kg of 30% caustic soda solution.

[0051] 将苯乙烯104千克一次性投入1000L搪瓷釜内;开动搅拌,升温至70°C,开始滴加30%过硫酸钠溶液840千克、溴化钠溶液和硫酸溶液;三种物料在8小时内同时加完,滴加过程中温度控制在65〜80°C,滴加完后,继续反应8小时,温度控制在65〜80°C;停搅拌,取样,检测合格即为反应终点;静置,分去油层,水层通冷降温至-10°C,析出芒硝晶体990千克,滤出固体后母液用于配制溴醇化所需的各种溶液。 [0051] 104 kg of styrene into the disposable 1000L enamel kettle; Stirring was heated to 70 ° C, the dropwise addition of a 30% solution of 840 kg of sodium persulfate, sodium bromide solution and a sulfuric acid solution; the three materials 8 hours while the addition was complete, the temperature control during the addition at 65~80 ° C, the dropwise addition, the reaction was continued for 8 hours at controlled temperature 65~80 ° C; stop stirring, sampling, testing is the endpoint of the reaction qualified; Still, the sub oil layer, the aqueous layer cooled through cooling to -10 ° C, 990 kg crystals precipitated Glauber's salt, the various solutions required bromo alkoxides mother liquor after the solid filtered for formulation. 将溴代苯乙醇一次性投入皂化釜内;开搅拌,控温45°C,开始滴加液碱;6小时加完,然后继续反应6小时,温度控制在40〜45°C ;反应结束后,静置半小时,检测合格即为反应终点;放出下层的回收溴化钠溶液,将料液放入成品罐内Γ溴化钠溶液经测试含量后添加新的溴化钠调配浓度至28.6%,继续用于溴醇化反应。 The disposable bromobenzene ethanol into the saponification reactor; open stirring, temperature 45 ° C, dropwise addition of caustic soda; 6 hours the addition was complete, then the reaction was continued for 6 hours at controlled temperature 40~45 ° C; after completion of the reaction , allowed to stand for half an hour, the reaction endpoint is the detection of qualified; lower discharge recovering sodium bromide solution, was placed in the feed solution was tested after adding content of the finished tank Γ sodium bromide sodium bromide new formulation to a concentration of 28.6% continue reaction for bromo alkoxides. 环氧苯乙烷收率89.6%。 Yield 89.6% styrene oxide. 图5是实施例2的反应路线图,图6是实施例2的工艺流程图。 FIG 5 is a reaction scheme of Example 2, FIG. 6 is a process flow diagram of the second embodiment.

[0052] 实施例3 [0052] Example 3

[0053] 配制30%硫酸溶液167千克,溴化钠溶液(含纯溴化钠103千克)380千克,20%液碱溶液200千克。 [0053] The formulated solution 167 kg 30% sulfuric acid, sodium bromide solution (containing 103 kg of pure sodium bromide) 380 kg, 200 kg of 20% caustic soda solution.

[0054] 将苯乙烯104千克一次性投入1000L搪瓷釜内;开动搅拌,升温至80°C,开始滴加70%叔丁基过氧化氢溶液200千克、溴化钠溶液和硫酸溶液;三种物料在6小时内同时加完,滴加过程中温度控制在65〜80°C ;滴加完后,继续反应6小时,温度控制在65〜80°C ;停搅拌,取样,检测合格即为反应终点静置,分去油层,水层通冷降温至_12°C,析出芒硝晶体308千克,滤出固体,母液继续用于配制溴醇化所需的各种溶液。 [0054] 104 kg of styrene into the disposable 1000L enamel kettle; Stirring was heated to 80 ° C, the dropwise addition of 70% t-butyl hydrogen peroxide solution 200 kg, a solution of sodium bromide and sulfuric acid; three kinds material simultaneously added over 6 hours at controlled temperature during the addition 65~80 ° C; after the dropwise addition, reaction was continued for 6 hours at controlled temperature 65~80 ° C; stop stirring, sampling, testing that is qualified end of the reaction was allowed to stand, points to the reservoir, the aqueous layer cooled through cooling to _12 ° C, 308 kg precipitated Glauber's salt crystals, the solid was filtered off, the mother liquor was continued for formulating various desired bromo alkoxides. 将溴代苯乙醇一次性投入皂化釜内;开搅拌,控温40°C,开始滴加液碱;5小时加完,然后继续反应5小时,温度控制在40〜45°C;反应结束后,静置半小时,检测合格即为反应终点;放出下层的回收溴化钠溶液,将料液放入粗品罐内;溴化钠溶液经测试含量后添加新的溴化钠调配浓度至27.1%,继续用于溴醇化反应。 The disposable bromobenzene ethanol into the saponification reactor; open stirring, temperature 40 ° C, dropwise addition of caustic soda; of 5 hours, and then the reaction was continued for 5 hours at controlled temperature 40~45 ° C; after completion of the reaction , allowed to stand for half an hour, the reaction endpoint is the detection of qualified; lower discharge recovering sodium bromide solution, the crude material was put into the tank; the content of the test solution was added the sodium bromide sodium bromide new formulation to a concentration of 27.1% continue reaction for bromo alkoxides. 粗品精馏,环氧苯乙烷收率70.8%。 The crude distillation, a yield of 70.8% styrene oxide.

[0055] 实施例4 [0055] Example 4

[0056] 配制20%硫酸溶液250千克,溴化钠溶液(含纯溴化钠103千克)330千克,20%液碱溶液200千克。 [0056] The formulated solution 250 kg 20% ​​sulfuric acid, sodium bromide solution (containing 103 kg of pure sodium bromide) 330 kg, 200 kg of 20% caustic soda solution.

[0057] 将苯乙烯104千克一次性投入1000L搪瓷釜内;开动搅拌,升温至80°C,开始加入过氧化二叔丁基150千克、溴化钠溶液和硫酸溶液;2小时内加完,滴加过程中温度控制在55〜60°C;滴加完后,继续反应6小时,温度控制在55〜60°C;停搅拌,取样,检测合格即为反应终点;静置,分去油层,水层通冷降温至_12°C,析出芒硝晶体312千克,滤出固体,母液用于配制溴醇化所需的各种溶液。 [0057] 104 kg of styrene into the disposable 1000L enamel kettle; Stirring was heated to 80 ° C, start adding 150 kg t-butyl peroxide, sodium bromide solution and a sulfuric acid solution; the addition was complete within 2 hours. during the addition the temperature controlled at 55~60 ° C; after the dropwise addition, reaction was continued for 6 hours at controlled temperature 55~60 ° C; stop stirring, sampling, testing end of the reaction that is qualified; Still, the sub oil the aqueous layer was cooled on cooling to _12 ° C, 312 kg precipitated Glauber's salt crystals, the solid was filtered off, the mother liquor was used to formulate various desired bromo alkoxides. 将溴代苯乙醇一次性投入皂化釜内;开搅拌,控温40°C,开始滴加液碱;5小时加完,然后继续反应5小时,温度控制在40〜45°C ;反应结束后,静置半小时,检测合格即为反应终点;放出下层的回收溴化钠溶液,将料液放入粗品罐内;溴化钠溶液经测试含量后添加新的溴化钠调配浓度至31.2%,继续用于溴醇化反应。 The disposable bromobenzene ethanol into the saponification reactor; open stirring, temperature 40 ° C, dropwise addition of caustic soda; of 5 hours, and then the reaction was continued for 5 hours at controlled temperature 40~45 ° C; after completion of the reaction , allowed to stand for half an hour, the reaction endpoint is the detection of qualified; lower discharge recovering sodium bromide solution, the crude material was put into the tank; the content of the test solution was added the sodium bromide sodium bromide new formulation to a concentration of 31.2% continue reaction for bromo alkoxides. 粗品精馏,环氧苯乙烷收率64.2%。 The crude distillation, a yield of 64.2% styrene oxide.

Claims (7)

1.一种废水零排放工艺制备环氧苯乙烷的方法,包括如下步骤: 1)苯乙烯在溴盐水溶液、硫酸和氧化剂存在下控温-15〜150°C进行溴醇化反应,反应结束后静置,得到废水一和油层一; 2)油层一加入碱溶液进行皂化反应,反应毕,分出油层二,得到环氧苯乙烷粗品及废水二,粗品经精馏提纯得到环氧苯乙烷成品; 3)废水二主要含有溴盐,经添加部分溴盐调配浓度至5〜50%后继续用于第一步溴醇化反应;将废水一降温析出硫酸盐;析出硫酸盐固体后的含溴盐废水再次用于配制溴醇化反应所用的溶液; 步骤I)所述的氧化剂是双氧水、过硫酸钠、叔丁基过氧化氢溶液以及过氧化二叔丁基。 1. A method for the preparation of zero discharge waste styrene oxide process, comprising the steps of: 1) a styrene -15~150 ° C temperature in an aqueous solution, sulfuric acid and oxidizing agent bromo alcoholate salt bromine reaction, the reaction after standing, to give a waste water reservoir and a; 2) oil was added a solution of an alkali saponification reaction, the reaction was completed, the oil layer was separated two, styrene oxide to give the crude two and wastewater, crude product purified by distillation to give ethylene benzene finished ethane; 3) two wastewater containing mainly bromide, the bromide salt was added after the formulation to a concentration of 5~50% portion continue the reaction for the first step-bromo alkoxides; a waste water cooling sulfate precipitation; the solid precipitated sulfate bromide containing waste water again for formulation bromo alcoholate solution used in the reaction; oxidant step I) is the hydrogen peroxide, sodium persulfate, t-butyl hydroperoxide and a solution of di-t-butyl peroxide.
2.按照权利要求1所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤I)所述的溴盐是溴化钠、溴化钾、溴化铵、溴化镁、溴化钙、其他碱金属的溴化物或其他碱土金属的溴化物中的一种或几种。 2. The method of zero discharge of wastewater styrene oxide was prepared according to the process according to claim 1, wherein step I) of the bromide is sodium bromide, potassium bromide, ammonium bromide, magnesium bromide , bromide, calcium bromide, other alkali metal bromide or an alkaline earth metal in the other one or more.
3.按照权利要求1所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤I)所述的苯乙烯:溴盐:酸:氧化剂=I: 0.5〜5: 0.5〜5: 0.5〜10,该比例为摩尔比,其中酸若是多元酸则以实际发挥作用的氢离子的摩尔数计。 3. The method of zero discharge of wastewater styrene oxide was prepared according to the process as claimed in claim 1, wherein the styrene step I) according to: bromide: acid: oxidizing agent = I: 0.5~5: 0.5~ 5: 0.5~10, the ratio is molar ratio, wherein the acid polyacid places if the actual moles of hydrogen ions play a role.
4.按照权利要求1所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤3)中的废水一采用降温、蒸发、反渗透或挥发浓缩的方法,使反应生成的盐析出。 4. The method of preparation of zero discharge of waste water to the styrene oxide as claimed in claim 1, characterized in that the waste water in step 3) using a cooling, evaporation, reverse osmosis or volatile method of concentrating the reaction of salt precipitation.
5.按照权利要求1所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤3)优选降温法使反应生成的盐析出。 5. The method of claim 1 prepared zero discharge waste styrene oxide process according to claim, wherein the step 3) that the cooling method is preferably precipitated salt produced by the reaction.
6.按照权利要求7所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤3)降温法是将废水一降温至-30〜25V。 6. The method of preparation of zero discharge of waste water according styrene oxide as claimed in claim 7, wherein the step 3) a waste water cooling method is lowered to -30~25V.
7.按照权利要求1所述的废水零排放工艺制备环氧苯乙烷的方法,其特征在于,步骤I)使用氧化剂时可以加入促进氧化效果的物质,铜、锰、铁、铬、镍或钒的盐。 7. The method of zero discharge of wastewater styrene oxide was prepared according to the process according to claim 1, wherein step I) using an oxidizing agent may be added to promote the oxidation effect of substances, copper, manganese, iron, chromium, nickel, or vanadium salt.
CN201010213560.7A 2010-06-30 2010-06-30 Method for preparing styrene oxide by waste water zero discharge process CN102311408B (en)

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