WO2006092085A1

WO2006092085A1 - A process for producing dihydroxy alcohol and polyol by cracking sorbitol

Info

Publication number: WO2006092085A1
Application number: PCT/CN2005/000475
Authority: WO
Inventors: Zhouwen Xu
Original assignee: Global Polyol Investments Limited
Priority date: 2005-03-01
Filing date: 2005-04-11
Publication date: 2006-09-08
Also published as: CN1683293A

Abstract

The invention relates to a process for producing C2-4 dihydroxy alcohol and polyol by cracking sorbitol in an aqueous phase, specially to a process for producing C2-4 dihydroxy alcohol and polyol by using corn as raw material to obtain sorbitol and then hydrocracking sorbitol. The process comprises hydrocracking sorbitol to obtain a mixture of C2-4 dihydroxy alcohol and polyol in the presence of sodium hydroxide and Ni/Ru cracking catalyst at high temperature and elevated pressure, and producing individual products by separating and refining. The process according to the invention has many advantages that the production route is novel, the process conditions are unique, several kinds of alcohol can be produced simultaneously, and the qualities of products are better than those produced by other processes. In addition, it's of significance in respect of raw material, because the process can use grain such as corn as raw material, i.e. using renewable resource instead of non-renewable resource.

Description

一种由山梨醇裂解生产二元醇和多元醇的方法技术领域 Method for producing diol and polyol by sorbitol cracking

本发明涉及一种由山梨醇水相裂解生产二元醇和多元醇的方法，特别是以谷物如玉来为原料制得山梨醇再由其加氢裂解生产乙二醇、丙二醇、丙三醇、丁二醇等二元醇和多元醇的方法。背景技术 The invention relates to a method for producing glycols and polyols by aqueous phase cracking of sorbitol, in particular to produce sorbitol from cereals such as jade, and then hydrocracking to produce ethylene glycol, propylene glycol, glycerol, A method of a glycol such as butanediol and a polyol. Background technique

目前市场上的二元醇、多元醇生产方法都是以石油为原料生产。例如以环氧乙烷为原料生产乙二醇，以环氧丙烷为原料生产丙二醇。这些醇市场应用量都非常大，例如乙二醇全世界年消费量为 1565万吨，每年都消耗大量的石油原料。基于目前石油短缺，价格上涨等因素，人们都在寻找一种可再生资源代替石油原料，这将会更有发展前景。随着农业技术的发展，粮食产量不断增加出现供过于求的局面，粮食深加工项目也比较有发展前景。玉米淀粉、糖蜜等都是山梨醇最好的原料，山梨醇进一步加工即可得到乙二醇、丙二醇、丙三醇、丁二醇等多种二元醇和多元醇。中国专利 CN 1246077A公开了一种"镍 /钌催化剂及用于水相反应的方法"，其中提到在该催化剂存在下的加氢反应，该反应包括将山梨醇转化成乙二醇、丙二醇和甘油，但没有具体的技术方案和实施方案。因此，本发明所述的由山梨醇生产 C₂.₄二元醇和多元醇具体生产方法的生产路线是新颖的，工艺条件是独特的。现有的文献尚未有报道过本发明如此全面和具体的生产路线和方法。发明内容 At present, the production methods of diols and polyols on the market are all produced from petroleum. For example, ethylene glycol is used as a raw material to produce ethylene glycol, and propylene oxide is used as a raw material to produce propylene glycol. These alcohols are used in a very large market. For example, ethylene glycol consumes 15.65 million tons per year, and consumes a large amount of petroleum raw materials every year. Based on current oil shortages, rising prices and other factors, people are looking for a renewable resource to replace petroleum raw materials, which will have more development prospects. With the development of agricultural technology, the situation of oversupply has been increasing due to the continuous increase in grain output, and the grain deep processing project has relatively promising prospects. Corn starch and molasses are the best raw materials for sorbitol, and sorbitol can be further processed to obtain various glycols and polyols such as ethylene glycol, propylene glycol, glycerin, and butylene glycol. Chinese Patent No. 1246077A discloses a "nickel/ruthenium catalyst and a process for the aqueous phase reaction", wherein a hydrogenation reaction in the presence of the catalyst is mentioned, which comprises converting sorbitol to ethylene glycol, propylene glycol and Glycerin, but there are no specific technical solutions and implementations. Thus, the production of sorbitol C dihydric and polyhydric alcohols specific production method _{_2.4} Production line according to the present invention is novel, unique process conditions. The existing literature has not yet reported such a comprehensive and specific production route and method of the present invention. Summary of the invention

本发明的目的在于提供一种由山梨醇水相裂解生产 C₂-₄二元醇和多元醇的方法，特别是以谷物如以玉米为原料生产山梨醇，再将山梨醇裂解生产二元醇如乙二醇、丙二醇、各种丁二醉异构体等和多元醇如丙三醇等的方法。本发明涉及一种由山梨醇水相裂解生产 C_2-4二元醇和多元醇的方法，该方法包括在氢氧化钠和镍 /钌裂解催化剂存在下，在水相中山梨醇在水溶液中的重量配比为 5-30%，山梨醇与氢氧化钠的摩尔比为 5-15： 1，将山梨醇加氢裂解生成 C₂.₄二元醇和多元醇的混合物，经分离精制后分别得到单一产品。按照本发明所述的由山梨醇水相裂解生产 C₂.₄二元醇和多元醇的方法，其中所述的加氢裂解在反应温度为 190-280°C，优选为 200-250 V , 最优选为 230°C，反应压力为 10-15Mpa，优选为 11.5-13Mpa, 最优选为 12Mpa下进行。在水相中山梨醇在水溶液中的重量配比优选为 25%; 山梨醇与氢氧化钠的摩尔比优选为 8 : 1；原料液 pH值为 11-13，优选为 12.3 ; 反应时间为 20-50分钟，优选为 30分钟。本发明所述的二元醇为乙二醇、丙二醇和各种丁二醇异构体，所述各种丁二醇异构体为 1， 2-丁二醇、 1， 3-丁二醇、 1， 4-丁二醇和 2， 3-丁二醇，所述的多元醇主要为丙三醇。按照本发明所述的由山梨醇水相裂解生产 C₂-₄二元醇和多元醇的方法，所述的将山梨醇进行加氢裂解生成的 C₂_₄二元醇和多元醇混合物的重量组成为：乙二醇 15-30%; 丙二醇 30-60%; 丙三醇 15-30; 各种丁二醇异构体 5-12%，其中， 1， 2-丁二醇约 3-6%， 1， 4-丁二醇 1-2%和 2， 3-丁二醇约 2-4°/。；剩余为其它物质，约占 3-16%，这些物质如甲醇约为 0.75-1.5%, 乙醇约为 0.75-1.5%，山梨醇约为 0.2-5%，有机酸盐约为 2-3%, 甲烷少量，其它物质约为 1-5%。本发明所述的山梨醇可以谷物为原料优选为玉米首先制成淀粉、经液化糖化生成葡萄糖、再加氢而制得。本发明所述的镍 /钌裂解催化剂为已知的用于将高碳多元醇裂解成低碳多元醇的裂解催化剂（详述参见美国专利 5,814, 112 和公开号 20020169344 ) , 但本发明的反应物和反应条件与上述的美国专利文件中所述的不同。本发明的二元醇和多元醇生产方法所采用的原材料为山梨醇，其可以是市场上购买的山梨醇，也可以是以谷物如玉米为原料，采用常规方法生产淀粉，经过液化糖化生成葡萄糖，再通过加氢生产出本发明所使用的山梨醇。本发明的基本原料为淀粉，例如可以将玉米转化成淀粉乳后，直接液化、糖化生产葡萄糖。生成葡萄糖溶液，在镍催化剂作用下高压加氢反应生产液体山梨醇，在裂解催化剂作用下，山梨醇进一步加氢裂解生成所述的二元醇和多元醇；或市场上购置山梨醇直接裂解制得所述醇类；也可以由市场上购置糖蜜直接加氢制得山梨醇，再由山梨醇裂解获得所述的二元醇和多元醇。下面列出反应式来说明： The object of the present invention is to provide a method for producing a C ₂ _-4 glycol and a polyol from the aqueous phase of sorbitol, in particular to produce sorbitol from cereals such as corn, and then cleavage of sorbitol to produce a glycol. A method of ethylene glycol, propylene glycol, various dihydrogen isomers, and the like, and a polyhydric alcohol such as glycerin. The present invention relates to a process for the production of a _C2-4 diol and a polyol from the aqueous phase of sorbitol, which comprises sorbitol in an aqueous solution in the presence of sodium hydroxide and a nickel/ruthenium cracking catalyst. ratio of 5 to 30% by weight, molar ratio of sorbitol and sodium hydroxide is 5-15: 1, the hydrocracking of sorbitol to generate a mixture of diols and polyols C ₂ _4, respectively, obtained after isolated and purified. Single product. Diols and polyols according to the method of _{_2.4} Sorbitol aqueous phase from the cleavage of C produced according to the present invention, wherein the cleavage of the hydrogenation reaction temperature is 190-280 ° C, preferably 200-250 V, most Preferably, it is 230 ° C, and the reaction pressure is 10-15 MPa, preferably 11.5-13 MPa, and most preferably 12 MPa. The weight ratio of sorbitol in the aqueous phase is preferably 25%; the molar ratio of sorbitol to sodium hydroxide is preferably 8:1; the pH of the raw material liquid is 11-13, preferably 12.3; the reaction time is 20 - 50 minutes, preferably 30 minutes. The diol of the present invention is ethylene glycol, propylene glycol and various butanediol isomers, and the various butanediol isomers are 1,2-butanediol, 1, 3-butanediol. 1, 4-butanediol and 2,3-butanediol, the polyol being mainly glycerol. A method for producing a C ₂ _-4 glycol and a polyol by cracking an aqueous phase of sorbitol according to the present invention, wherein the weight composition of the mixture of C ₂ - ₄ glycol and polyol formed by hydrocracking sorbitol It is: ethylene glycol 15-30%; propylene glycol 30-60%; glycerol 15-30; various butanediol isomers 5-12%, wherein 1, 2-butanediol is about 3-6% 1, 1, 4-butanediol 1-2% and 2, 3-butanediol about 2-4 ° /. The rest are other substances, about 3-16%, such as methanol is about 0.75-1.5%, ethanol is about 0.75-1.5%, sorbitol is about 0.2-5%, organic acid salt is about 2-3%. , a small amount of methane, other substances are about 1-5%. The sorbitol according to the present invention can be obtained by using corn as a raw material, preferably corn firstly made into starch, liquefied and saccharified to form glucose, and then hydrogenated. The nickel/ruthenium cracking catalyst of the present invention is a known cracking catalyst for cracking a high carbon polyol into a low carbon polyol (for details, see U.S. Patent No. 5,814,112 and Publication No. No.20020169344), but the reaction of the present invention The materials and reaction conditions are different from those described in the above-mentioned U.S. patent documents. The raw material used in the method for producing diol and polyol of the present invention is sorbitol, which may be commercially available sorbitol, or may be obtained by using a method such as corn as a raw material to produce starch by liquefaction and saccharification to form glucose. The sorbitol used in the present invention is produced by hydrogenation. The basic raw material of the present invention is starch. For example, after converting corn into starch milk, direct liquefaction and saccharification can be used to produce glucose. Generating a glucose solution, producing a liquid sorbitol by a high pressure hydrogenation reaction under the action of a nickel catalyst, and further hydrocracking the sorbitol to form the diol and the polyol under the action of a cracking catalyst; or directly preparing a sorbitol by market for cleavage The alcohols may also be obtained by directly hydrogenating the molasses to obtain sorbitol, and then cleavage by sorbitol to obtain the diol and the polyol. The reaction formulas are listed below to illustrate:

1、葡萄糖的生产 1. Production of glucose

淀粉酶、糖化酶 Amylase, glucoamylase

:6 。05 nC₆H₁₂0₆ 淀粉葡萄糖 :6. 05 nC ₆ H ₁₂ 0 ₆ starch glucose

2、山梨醇的生产 2, the production of sorbitol

镍催化剂 C₆H₁₂O₆ + H, lOMpa 150-160 C₆H₁₄O6 Nickel catalyst C ₆ H ₁₂ O ₆ + H, lOMpa 150-160 C ₆ H ₁₄ O6

山梨醇以山梨醇为原料加氢得到相应醇。 Sorbitol is hydrogenated from sorbitol to give the corresponding alcohol.

、乙二醇： , ethylene glycol:

催化剂 Catalyst

2 H₂ 230-250 °C , 10-15MPa 3C₂H₆O2 山梨醇乙二醇 2 H ₂ 230-250 ° C , 10-15 MPa 3C ₂ H ₆ O2 Sorbitol Glycol

2)、丙二醇： 2), propylene glycol:

催化剂 Catalyst

C₆H₁₄O₆ + 3H₂ 230-250'C , 10-15MPa 2C₃H₈O₂ + 2H₂O 山梨醇氢 1， 2丙二醇水 C ₆ H ₁₄ O ₆ + 3H ₂ 230-250'C , 10-15MPa 2C ₃ H ₈ O ₂ + 2H ₂ O Sorbitol Hydrogen 1, 2 Propylene Glycol Water

3 )、丙三醇： 3), glycerol:

催化剂 Catalyst

C₆Hi₄O₆ + 3H₂ 230-250 °C , 10-15MPa 2C₃H₈O₃ C ₆ Hi ₄ O ₆ + 3H ₂ 230-250 °C , 10-15MPa 2C ₃ H ₈ O ₃

山梨醇氢丙三醇 Sorbitol hydrogen glycerol

4)、丁二醇: 4), butanediol:

催化剂 Catalyst

C₆Hi₄O + 2H₂ 230-250'C , 10-15MPa C₄H₁₀O₂ + C₂H₆O₂+ 2H₂O 山梨醇氢各种丁二醇乙二醇水丁二醇的同分异构体有四种: C ₆ Hi ₄ O + 2H ₂ 230-250'C , 10-15MPa C ₄ H ₁₀ O ₂ + C ₂ H ₆ O ₂ + 2H ₂ O Sorbitol hydrogen various butanediol ethylene glycol water butanediol There are four types of isomers:

C ₂CHCH₂

C ₂ CHCH ₂

2,3-丁二醇 1,4-丁二醇 1,3-丁二醇 1，2-丁二醇本发明可由谷物如玉米为原料生产山梨醇，其生产方法如下: 为 11-13，最佳为 12.3; 2,3-Butanediol 1, 4-butanediol 1, 3-butanediol 1,2-butanediol The present invention can produce sorbitol from cereals such as corn, and the production method thereof is as follows: For 11-13, the best is 12.3;

2) 加热： 2) Heating:

将配制后的原料液混合物料加热至约 180-220°C，以供给下一步的裂解反应用； The prepared raw material mixture is heated to about 180-220 ° C for supply to the next cracking reaction;

3) 裂解反应： 3) Cracking reaction:

裂解是整个过程中最关键的步骤，该裂解反应的反应温度为 190-280 , 反应压力为 10-15Mpa，反应时间约为 20-50分钟。达到条件的山梨醇发生化学反应生成本发明所需要的二元醇和多元醇； Cleavage is the most critical step in the process. The reaction temperature is 190-280, the reaction pressure is 10-15 MPa, and the reaction time is about 20-50 minutes. The sorbitol that meets the conditions undergoes a chemical reaction to form the diol and polyol required by the present invention;

4) 混合物脱水： 4) Dehydration of the mixture:

将反应生成物中的水全部脱除，这样可以在分离过程中得到较纯净的组分，脱水可通过脱水精镏塔连续进行； The water in the reaction product is completely removed, so that a relatively pure component can be obtained in the separation process, and the dehydration can be continuously carried out through the dehydration column.

5 ) 脱重组分： 5) Weight loss components:

将反应物中一些较重的组分 (包括有机酸盐)除去，以便获得本发明所需的二元醇和多元醇纯净组分，脱重组分可通过脱重精镏塔连续进行； Some of the heavier components (including organic acid salts) in the reactants are removed to obtain the diol and polyol neat components required for the present invention, and the de-weighting components can be continuously passed through the de-concentration column;

6 ) 分离 6) Separation

将脱水、脱重组分后的二元醇和多元醇通过多个产品精镏塔如填料塔可逐个地将其分离，分别得到本发明所需要的纯净组份乙二醇、丙二醇、丙三醇、各种丁二醇异构体等。附图说明 The diol and the polyol after dehydration and degreasing components can be separated one by one through a plurality of product condensing towers, such as a packed column, to obtain the pure components of ethylene glycol, propylene glycol and glycerol, which are required for the present invention, respectively. Various butanediol isomers and the like. DRAWINGS

图 1 为本发明二元醇和多元醇生产方法的示意图。以下结合图 1 具体说明本发明所述的二元醇和多元醇的生产方法。如果包括由淀粉乳生产山梨醇和由甲醇裂解制氢的工序，本发明装置共分四个部分:即原料接收、储运成品包装工段；甲醇裂解、变压按常规方法，将玉米转化成淀粉乳，在淀粉酶和糖化酶存在下，与水生成 70-76%的液体葡萄糖，于约 24 °C下冷却结晶，离心分离后得到约 60%的潮糖溶液，然后，在通常的镍催化剂存在下，于 150- 16(TC 和压力 10 Mpa与氢气进行加氢反应制得山梨醇。本发明可由甲醇裂解生产氢气，其生产方法如下：按常规方法，将甲醇和脱盐水按规定比例混合，经加压、预热、汽化过热至反应温度为 220-280°C，于反应压力为约 0.9 Mpa, 在催化剂存在下，进行转化反应，得到转化气，其中氢气含量为 73-74.5%。再将高温转化气进行冷却、冷凝至 40Ό以下，经常规方法精制后得 99.5%的氢氢，以待使用。本发明上述的由玉米为原料生产山梨醇和由甲醇裂解生产氢气的工艺优点如下： BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of the process for producing diols and polyols of the present invention. Hereinafter, a method for producing a glycol and a polyol according to the present invention will be specifically described with reference to FIG. If the process includes the production of sorbitol from starch milk and the hydrogen production from methanol cracking, the device of the invention is divided into four parts: raw material receiving, storage and transportation packaging section; methanol cracking, pressure transformation According to the conventional method, the corn is converted into starch milk, 70-76% liquid glucose is formed with water in the presence of amylase and saccharification enzyme, and the crystal is cooled at about 24 ° C, and about 60% of the intensive sugar is obtained by centrifugation. The solution is then subjected to hydrogenation reaction with hydrogen at 150 to 16 (TC and a pressure of 10 Mpa in the presence of a usual nickel catalyst to produce sorbitol. The present invention can produce hydrogen by methanol cracking, and the production method thereof is as follows: The methanol and the desalted water are mixed in a predetermined ratio, superheated by pressurization, preheating, vaporization to a reaction temperature of 220-280 ° C, and the reaction pressure is about 0.9 Mpa, and in the presence of a catalyst, a conversion reaction is carried out to obtain a reformed gas. The hydrogen content is 73-74.5%. The high-temperature reformed gas is cooled and condensed to below 40 ,, and refined by a conventional method to obtain 99.5% of hydrogen hydrogen to be used. The above-mentioned corn-based raw material for producing sorbitol and The advantages of methanol cracking to produce hydrogen are as follows:

1 . 本工艺釆用间隙式反应，生产灵活性强，可采用不同原料生产不同级别的山梨醇；采用高压加氢反应，反应时间短、产率高，确保生产高质量的山梨醇；本工艺可使生产成本大为降低； 1. The process adopts gap reaction, has strong production flexibility, and can produce different grades of sorbitol by using different raw materials; adopting high-pressure hydrogenation reaction, short reaction time and high yield, ensuring high-quality sorbitol production; Can greatly reduce production costs;

2. 本工艺采用甲醇裂解制氢技术，与水电解制氢相比，氢气成本减少 2/3。本发明的 C₂.₄二元醇和多元醇生产方法包括如下步骤： 1) 配料混合： 2. This process uses methanol cracking hydrogen production technology, which reduces hydrogen cost by 2/3 compared with hydrogen electrolysis. . C _₂₄ according to the present invention, diols and polyols production process comprising the following steps: 1) mixing the ingredients:

将山梨醇与水及氢氧化钠按一定比例进行混合；为了达到有效的反应效果，混合时最好将山梨醇在水溶液中的重量配比控制在山梨醇含量约为 5-30%，山梨醇与碱的摩尔比为 5-15: 1，原料液 pH值吸附、解析气回收工段；反应工段；脱水、分离和产品精制工段四个部分。原料接收主要接收淀粉乳转化的的葡萄糖浆或直接购买的糖蜜生产山梨醇、另外还有一些辅助材料碱、甲醇等原料，制氢工段是利用甲醇制得合格氢气供反应用，反应工段是本装置的核心工段，山梨醇、氢气等原料于高温、高压条件下，在此反应器中实现化学反应。生成各种需要的产品。分离、精制工段是利用各产品不同沸点进行分离，得到相应的产品，如丙二醇、乙二醇、丙三醇，各种丁二醇的同分异构体，以及甲醇、乙醇等副产品。本发明是以山梨醇为原料，经过高温、高压裂解后得到乙二醇、丙二醇、丙三醇、丁二醇等相关的二元醇和多元醇。本发明的生产方法优点在于生产路线新颖，工艺条件独特，易操作，工艺简单，并可同时生产出多种二元醇和多元醇，产品质量好。并可以谷物如玉米为原料生产山梨醇，即可以可再生资源代替不可再生资源，产品质量性能比其他方法生产的醇类要好，而其生产及原料方面有着极大优势。有着下述的历史意义、社会意义与现实意义。一、以谷物如玉米为原料生产所述的二元醇和多元醇具有深远的历史意义及社会意义。能源开发、资源利用与环境保护相互协调发展，将是 21世纪世界经济发展的基础。该项目是我公司与美国 IPCI公司进行合作，在小试和中试取得成功的基础上，进一步扩大中试规模，摸索工艺、技术和装备的相关工程化数据为大规模生产奠定了基础。现已实现工业化生产。该课题工程研究的突破对于解决目前石油资源短缺、农副产品过剩、环境污染加剧等问题具有现实意义和社会意义，当然通过资源合理利用对我国经济可持续发展和生态环境建设有着下述更深远的意义： Mixing sorbitol with water and sodium hydroxide in a certain ratio; in order to achieve an effective reaction effect, it is preferred to control the weight ratio of sorbitol in aqueous solution to about sorbitol content of about 5-30%, sorbitol when mixing. The molar ratio to the base is 5-15: 1, the pH of the raw material solution Adsorption, analytical gas recovery section; reaction section; dehydration, separation and product refinement section four parts. The raw material receives glucose syrup which is mainly converted from starch milk or directly purchases molasses to produce sorbitol, and also has some auxiliary materials such as alkali and methanol. The hydrogen production section uses methanol to obtain qualified hydrogen for reaction, and the reaction section is In the core section of the plant, sorbitol, hydrogen and other raw materials are subjected to chemical reactions in the reactor under high temperature and high pressure conditions. Generate a variety of products you need. Separation and refining sections are separated by different boiling points of each product to obtain corresponding products such as propylene glycol, ethylene glycol, glycerol, isomers of various butanediols, and by-products such as methanol and ethanol. The invention uses sorbitol as a raw material, and obtains related glycols and polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, butanediol after high temperature and high pressure cracking. The production method of the invention has the advantages of novel production route, unique process conditions, easy operation, simple process, and simultaneous production of various glycols and polyols, and the product quality is good. It can produce sorbitol from grains such as corn, which means that renewable resources can replace non-renewable resources. The quality and performance of products are better than those produced by other methods, and its production and raw materials have great advantages. It has the following historical, social and practical significance. First, the production of the diols and polyols from grains such as corn has far-reaching historical and social significance. The coordinated development of energy development, resource utilization and environmental protection will be the basis for the development of the world economy in the 21st century. The project is based on the cooperation between the company and the US IPCI company. On the basis of the success of the pilot and pilot tests, the scale of the pilot scale is further expanded, and the relevant engineering data of the process, technology and equipment are explored to lay the foundation for mass production. Industrial production has now been achieved. The breakthrough in engineering research of this subject has practical significance and social significance for solving the current shortage of petroleum resources, excess agricultural and sideline products, and intensifying environmental pollution. Of course, through the rational use of resources, the following is more profound for the sustainable development of China's economy and the construction of ecological environment. significance:

1)利用可再生资源来替代不可再生资源生产相关产品以解决人类面临的能源枯竭危机。上一世纪世界经济的发展主要以不可再生的、廉价的石油资源作为能源和生产原料。石油的开发和利用迅速推动了世界经济的发展，给人类物质生活带来了空前的便利和繁荣。但石油资源是不可再生的，地球上的储量是有限的，据有关统计报导，世界石油每年开采量与新探明的储量关系是 .4: 1 , 人类正在面临不可再生石油资源迅速走向枯竭的危机。开发新能源、寻找可再生资源的替代，资源合理利用、保护人类生存环境，是维持世界繁荣和发展的基础。本发明则是对此作出了贡献。我国是石油资源短缺国，每年需大量进口，进口量约 6000 万吨 / 年，专家预测到 2010年进口量将达到 1亿吨 /年。巨大的石油迸口需要大量外汇，这将对我国国民经济产生严重影响。如果以淀粉为原料替代石油生产基本有机化工产品，对于解决我国石油资源短缺问题、节省大量外汇、实行可持续发展战略、加速推进现代化建设，全面实现小康社会有着深远的现实意义和社会意义。 1) Renewable resources are used to replace non-renewable resources to produce related products to solve the energy depletion crisis facing humanity. The development of the world economy in the last century was mainly based on non-renewable and cheap petroleum resources as energy and production materials. The development and utilization of oil has rapidly promoted the development of the world economy and brought unprecedented convenience and prosperity to human material life. However, oil resources are non-renewable. The reserves on the earth are limited. According to relevant statistics, the relationship between the annual exploitation of world oil and newly discovered reserves is .4: 1 . Human beings are facing the rapid depletion of non-renewable petroleum resources. crisis. The development of new energy sources, the search for alternatives to renewable resources, the rational use of resources, and the protection of the human living environment are the foundation for maintaining world prosperity and development. The present invention has contributed to this. China is a country with a shortage of oil resources. It needs a large amount of imports every year. The import volume is about 60 million tons/year. Experts predict that the import volume will reach 100 million tons/year by 2010. A huge oil raft needs a lot of foreign exchange, which will have a serious impact on our national economy. If starch is used as a raw material to replace petroleum production of basic organic chemical products, it has far-reaching practical and social significance for solving China's shortage of petroleum resources, saving a large amount of foreign exchange, implementing a sustainable development strategy, and accelerating modernization.

2)依靠高科技推进农业产业化实现可持续发展 2) Relying on high technology to promote agricultural industrialization to achieve sustainable development

全世界年产玉米约 5.5亿吨，美国年产玉米约 2.5亿吨，居世界首位，中国年产玉米约 1.2亿吨，居世界第二位。中国东北地区是世界黄金玉米带，玉米主产区，其中吉林省年产玉米约 2000万吨，居全国之首。依靠高科技开发、以玉米为原料生产有机化工产品的技术，对增加玉米附加值、提高农民种粮积极性、减少国家财政负担、增加就业机会，实现农业产业化，推动农村乃至全省经济的可持续发展有着十分重要的意义。 The annual output of corn in the world is about 550 million tons. The annual output of corn in the United States is about 250 million tons, ranking first in the world. China has an annual output of about 120 million tons of corn, ranking second in the world. Northeast China is the world's yellow gold corn belt, the main corn producing area, of which Jilin Province has an annual output of about 20 million tons of corn, ranking first in the country. Relying on high-tech development and using corn as raw material to produce organic chemical products, it will increase the added value of corn, increase the enthusiasm of farmers to grow grain, reduce the national financial burden, increase employment opportunities, realize agricultural industrialization, and promote the economy of rural areas and even the whole province. Sustainable development is of great significance.

3)保护生态环境 3) Protecting the ecological environment

环保问题越来越受到全世界人民和各国政府重视，我国亦不例外。最近，国家为保护生态环境，实现可持续发展战略，正在抓紧制订和出台企业清洁生产的政策和法规。石油化工产品在给人类带来方便的同时也给人类带来灾难 --—生态环境受到破坏！石油化工行业从原料开釆到生产及产品一般都会给人类生存环境带来污染，破坏地球生态环境；如原油在开采过程中使地球植被遭到破坏，生产过程中带来 "三废"，使用过的产品垃圾不降解带来 "白色污染 " 等；而以玉米为原料深加工成有机化工产品，原料是可再生的资源，产品可降解回归自然，在应用上也没有石油化工产品带来的那些毒性，大大减少石油化工行业带来的环境污染和对人类健康造成的危害，有利于保护生态环境为人类造福。 Environmental issues are increasingly being valued by people and governments around the world, and China is no exception. Recently, in order to protect the ecological environment and achieve sustainable development strategies, the state is speeding up the formulation and introduction of policies and regulations for cleaner production. Petrochemical products bring convenience to human beings while also bringing disasters to human beings - the ecological environment is destroyed! Petrochemical industry starts from raw materials When it comes to production and products, it will generally pollute the human living environment and destroy the earth's ecological environment. For example, if the crude oil destroys the earth's vegetation during the mining process, it will bring "three wastes" in the production process, and the used product waste will not degrade the belt. Come to "white pollution", etc.; and use corn as raw material for deep processing into organic chemical products, raw materials are renewable resources, products can be degraded and returned to nature, and there is no toxicity brought by petrochemical products in application, which greatly reduces the petrochemical industry. The environmental pollution caused by it and the harm to human health are conducive to the protection of the ecological environment for the benefit of mankind.

4)生产安全性高，有利于劳动保护 4) High production safety, which is conducive to labor protection

实现安全文明生产，保护生产人员的安全，符合国家和广大人民的利益。利用石油生产的基础有机化工产品，从基本原理上看，大多是以碳氢化合物为主要原料在高温、高压状态下，通过催化、裂化、氧化、加氢、分离等过程进行生产。生产过程大多属易燃、易爆、有毒过程，对生产人员构成威胁，不利于劳动保护。利用淀粉生产有机化工产品过程则是以液化、糖化、加氢、裂化、分离等过程，生产工艺及设备相对简单，生产安全性相对高，有利于劳动保护。二、现实意义影响化工醇发展的主要因素是技术问题及国际粮食价格和石油价格。近五年的国际市场玉米价格（平均价为 103美元 /吨）非常稳定。石油价格，由于欧佩克经过近三十年的狂热和低迷之后，已形成了较符合现实的且具共同理解和信任的油价标准（25 $ /桶左右）。但随着石油贮藏量的减少，最终将走向枯竭的总趋势，国际石油价格的总趋势是上升的势头，随着海湾战争， ***战争的爆发，石油价格更加不稳定，尤其 2004年石油上涨出现了历年来少有的价格（50 $ /桶以上）。这种石油价格的波动，直接影响下游产品的稳定性，成本升高，原料来源紧张等。对后道工序的加工，市场供求的稳定都造成影响。而以玉米为原料，在成本及原料供应上都相对稳定，在成本上也较低。应该说以粮食如玉米为原料生产化工醇是一件利国利民的大好事。这个项目的成功与扩大，将对整个化工行业是一个很好的补充。具体实施方式 Achieving safe and civilized production and protecting the safety of production personnel is in the interest of the country and the people. Basically, the basic organic chemical products produced by petroleum are produced by processes such as catalysis, cracking, oxidation, hydrogenation, and separation under the conditions of high temperature and high pressure, mainly using hydrocarbons as the main raw materials. Most of the production process is flammable, explosive, and toxic, posing a threat to production personnel and not conducive to labor protection. The process of producing organic chemical products by using starch is liquefaction, saccharification, hydrogenation, cracking, separation, etc. The production process and equipment are relatively simple, and the production safety is relatively high, which is beneficial to labor protection. Second, the main factors affecting the development of chemical alcohol are technical issues and international food prices and oil prices. The price of corn in the international market in the past five years (average price of $103/ton) is very stable. The price of oil, due to the enthusiasm and downturn of OPEC for nearly three decades, has formed a more realistic and common understanding and trust in oil prices (about 25 $ / barrel). However, with the reduction of oil storage, the general trend of depletion will eventually lead to a general trend of international oil prices. With the Gulf War and the outbreak of the Iraq war, oil prices are more unstable, especially in 2004. A rare price (50 $ / barrel or more) over the years. This fluctuation in oil prices directly affects the stability of downstream products, rising costs, and tight sources of raw materials. The processing of the subsequent processes and the stability of the market supply and demand have an impact. Corn is used as raw material, which is relatively stable in terms of cost and raw material supply, and low in cost. It should be said that the production of chemical alcohol by using grain, such as corn, is a good thing for the country and the people. This The success and expansion of the project will be a good complement to the entire chemical industry. detailed description

实施例 1 Example 1

1 . 山梨醇的生产： 1. Production of sorbitol:

将 1000公斤玉米转化成淀粉乳（干基 700公斤），在淀粉酶和糖化酶存在下，与水生成约 742公斤 70%的液体葡萄糖，于 24°C下冷却结晶，离心分离后得到 865公斤 60%的潮糖溶液，然后，在镍催化剂存在下，于 156Ό和约 10 Mpa与氢氢进行加氢反应制得 860公斤山梨醇，以待使用。 Convert 1000 kg of corn into starch milk (700 kg dry basis), and in the presence of amylase and glucoamase, about 742 kg of 70% liquid glucose is formed with water, cooled at 24 ° C, and centrifuged to obtain 865 kg. 60% of the intensive sugar solution is then subjected to hydrogenation reaction with hydrogen hydrogen at 156 Torr and about 10 Mpa in the presence of a nickel catalyst to obtain 860 kg of sorbitol for use.

2. 甲醇的生产： 2. Production of methanol:

将 325公斤 /小时甲醇和 183公斤 /小时脱盐水混合，经加压、预热、汽化过热至反应温度为 260°C，于反应压力约 0. 9 Mpa, 在催化剂存在下，进行转化反应，得到约 900Nm³/小时转化气，其中氢气含量为 73-74.5%。再将高温转化气进行冷却、冷凝至 40°C以下，经常规方法精制后得 99. 5%的氢氢，以待使用。 Mixing 325 kg / h of methanol and 183 kg / h of demineralized water, pressurized, preheated, vaporized and superheated to a reaction temperature of 260 ° C, at a reaction pressure of about 0. 9 Mpa, in the presence of a catalyst, the conversion reaction, Approximately 900 Nm ³ /hour of reformed gas was obtained with a hydrogen content of 73-74.5%. The 5% hydrogen hydrogen is used for further purification. The high-temperature reformed gas is cooled and condensed to below 40 ° C.

3. C₂-₄二元醇和丙三醇的生产： 3. Production of C ₂ _-4 glycols and glycerol:

取 1000公斤 /小时原料 70%山梨醇加水 1800公斤 /小时稀释至 25% 与 4%氢氧化钠以摩尔比 8 : 1混合后，将原料液的 PH值调至 13 , 原料液经预热器预热至 176°C，然后，进入反应器，在镍 /钌裂解催化剂作用下与甲醇裂解制得的氢气在高温 230°C、高压 12 Mpa下发生裂解反应，得到 2800公斤 /小时反应产物，其为含有乙二醇、 1,2-丙二醇、丙三醇、 1,2-丁二醇、 2,3-丁二醇、 1,4-丁二醇、甲醇、乙醇、甲垸等的混合产物。一些未转化的山梨醇及反应过程中产生的重组分经精馏分离后返回到山梨醇原料配制工序进行重新配制,进一步裂解得到相应组分，与氢解产品混合一起进入产品贮罐，待进入分离工序。裂解产物的组成如下:

将 2800公斤 /小时所得的上述组成的裂解产物,经脱水、脱重组分工序将产物中的水分和重组分如甲酸盐、乙酸盐和丙酸盐等脱除，然后通过多个填料产品精镏塔进行所述醇类的分离，分离后得到各种醇类的单一产品以及甲醇和乙醇等副产品。实施例 2: 除了采用购买的山梨醇和氢氢作原料之外，其它按照与实施例 1 相同的方法生产所述的各种所述醇类。 Take 1000 kg / hour of raw material 70% sorbitol plus water 1800 kg / hour diluted to 25% and 4% sodium hydroxide in a molar ratio of 8 : 1 mixed, the pH of the raw material liquid is adjusted to 13, the raw material liquid through the preheater Preheating to 176 ° C, and then entering the reactor, under the action of nickel / hydrazine cracking catalyst and hydrogen produced by methanol cracking at a high temperature of 230 ° C, high pressure 12 Mpa cracking reaction, to obtain 2800 kg / hour reaction product, It is a mixture containing ethylene glycol, 1,2-propanediol, glycerol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, formamidine, and the like. product. Some unconverted sorbitol and heavy components produced during the reaction are separated by rectification and returned to the sorbitol raw material preparation process for reconstitution, further cracking to obtain the corresponding components, and mixed with the hydrogenolysis product into the product storage tank, to be entered Separation process. The composition of the cleavage product is as follows:

The cleavage product of the above composition obtained at 2800 kg/hr is subjected to a process of dehydration and de-weighting, and the moisture and heavy components such as formate, acetate and propionate in the product are removed, and then passed through a plurality of filler products. The fine column separates the alcohols, and after separation, a single product of various alcohols and by-products such as methanol and ethanol are obtained. Example 2: The various alcohols described were produced in the same manner as in Example 1 except that the purchased sorbitol and hydrogen hydroxide were used as raw materials.

Claims

权利要求书: Claims:

1. 一种由山梨醇水相裂解生产 c₂-₄二元醇和多元醇的方法，该方法包括在氢氧化钠和镍 /钌裂解催化剂存在下，在水相中山梨醇在水溶液中的重量配比为 5-30%，山梨醇与氢氧化钠的摩尔比为 5-15 : 1，将山梨醇加氢裂解生成 C₂.₄二元醇和多元醇的混合物，经分离精制后分别得到单一产品。 A process for the production of c ₂ _-4 glycols and polyols by aqueous phase cracking of sorbitol, the method comprising the weight of sorbitol in an aqueous solution in the presence of sodium hydroxide and a nickel/ruthenium cracking catalyst ratio of 5-30%, molar ratio of sorbitol and sodium hydroxide is 5-15: 1, the hydrocracking of sorbitol to generate a mixture of diols and polyols C ₂ _4, respectively, after a single separation and purification. product.

2. 根据权利要求 1所述的由山梨醇水相裂解生产 C₂_₄二元醇和多元醇的方法，其特征在于所述的加氢裂解在反应温度为 190-280°C，优选为 200-250°C，最优选为 230 °C，反应压力为 10-15Mpa，优选为 11.5-13Mpa，最优选为 12Mpa下进行。 2. Process for the production of C ₂ _-4 glycols and polyols by aqueous sorbitol phase cracking according to claim 1, characterized in that the hydrocracking is carried out at a reaction temperature of from 190 to 280 ° C, preferably 200 -250 ° C, most preferably 230 ° C, the reaction pressure is 10-15 MPa, preferably 11.5-13 MPa, most preferably 12 MPa.

3. 根据权利要求 1所述的由山梨醇水相裂解生产 C₂_₄二元醇和多元醇的方法，其特征在于在水相中山梨醇在水溶液中的重量配比为 25%, 山梨醇与氢氧化钠的摩尔比为 8: 1。 3. Process for the production of C ₂ _-4 glycols and polyols by aqueous phase decomposition of sorbitol according to claim 1, characterized in that the weight ratio of sorbitol in aqueous solution is 25% in the aqueous phase, sorbitol The molar ratio to sodium hydroxide is 8:1.

4. 根据权利要求 1-3任一项所述的由山梨醇水相裂解生产 ₂.₄二元醇和多元醇的方法，其特征在于原料液 pH值为 11-13，反应时间为 20-50分钟。 4. The method of cracking the aqueous phase from the production of sorbitol _{_2.4} diols and polyols according to any one of claims 1-3, characterized in that the pH of starting material solution 11-13, the reaction time from 20 to 50 minute.

5. 根据权利要求 4所述的由山梨醇水相裂解生产 C₂_₄二元醇和多元醇的方法，其特征在于原料液 pH值为 12.3，反应时间为 30分钟。 The method for producing C ₂ - ₄ glycol and polyol by sorbitol aqueous phase cracking according to claim 4, wherein the raw material liquid has a pH of 12.3 and a reaction time of 30 minutes.

6. 根据权利要求 1-3任一项所述的由山梨醇水相裂解生产 C₂.₄二元醇和多元醇的方法，其特征在于所述的二元醇为乙二醇、丙二醇和各种丁二醇异构体，所述的多元醇为丙三醇。 The diols and polyols method according to any one of claims 1-3 the aqueous phase by cleavage of sorbitol produced C _2. ₄ as claimed in claim wherein said dihydric alcohol is ethylene glycol, propylene glycol and various A butanediol isomer, the polyol being glycerol.

7. 根据权利要求 6所述的由山梨醇水相裂解生产 C₂-₄二元醇和多元醇的方法，其特征在于所述的各种丁二醇异构体为 1， 2-丁二醇、 1， 3-丁二醇、 1， 4-丁二醇和 2， 3-丁二醇。 Sorbitol according to claim aqueous phase from the cleavage of the C ₂ Production of 6 - diols and polyols _4, characterized in that the various isomers of butylene glycol 1,2-butanediol , 1, 3-butanediol, 1, 4-butanediol and 2,3-butanediol.

8. 根据权利要求 1-3任一项所述的由山梨醇水相裂解生产 0₂-₄二元醇和多元醇的方法，其特征在于所述的山梨醇进行加氢裂解生成 C₂_₄ 二元醇和多元醇混合物的重量组成为： The method for producing a 0 ₂ _-4 diol and a polyhydric alcohol by aqueous sorbitol cleavage according to any one of claims 1 to 3, wherein the sorbitol is hydrocracked to form C ₂ _ ₄ The weight composition of the glycol and polyol mixture is:

乙二醇 15-30%，丙二醇 30-60%, 丙三醇 15-30，各种丁二醇异构体 5-12%，剩余为其它物质。 Ethylene glycol 15-30%, propylene glycol 30-60%, glycerol 15-30, various butanediol isomers 5-12%, and the rest are other substances.

9. 根据权利要求 1-3任一项目所述的由山梨醇水相裂解生产 C₂-₄ 二元醇和多元醇的方法，其特征在于所述的山梨醇是以谷物为原料首先制成淀粉、经液化糖化生成葡萄糖、再加氢而制得。 ₂ Sorbitol aqueous phase from the cleavage of C 9. The production of an item according to any claim 1-3 ₄ - diols and polyols, characterized in that the sorbitol is a cereal starch material is first formed It is obtained by liquefaction saccharification to produce glucose and hydrogenation.

10. 根据权利要求 9所述的由山梨醇水相裂解生产 C₂.₄二元醇和多元醇的方法，其特征在于所述的谷物为玉米。 The method of producing a sorbitol aqueous phase cracking C _2. ₄ diols and polyols as claimed in claim 9, wherein said cereal is maize.