WO2016045583A1 - 一种制备二元醇的方法 - Google Patents

一种制备二元醇的方法 Download PDF

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Publication number
WO2016045583A1
WO2016045583A1 PCT/CN2015/090321 CN2015090321W WO2016045583A1 WO 2016045583 A1 WO2016045583 A1 WO 2016045583A1 CN 2015090321 W CN2015090321 W CN 2015090321W WO 2016045583 A1 WO2016045583 A1 WO 2016045583A1
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Prior art keywords
parts
glycol according
sugar
glycol
acid
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PCT/CN2015/090321
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English (en)
French (fr)
Inventor
刘菁
齐红彬
任海彧
普拉卡因德拉
石昱
Original Assignee
长春美禾科技发展有限公司
可口可乐公司
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Publication date
Priority to EP19206794.0A priority Critical patent/EP3653595B1/en
Priority to KR1020237038417A priority patent/KR20230159620A/ko
Application filed by 长春美禾科技发展有限公司, 可口可乐公司 filed Critical 长春美禾科技发展有限公司
Priority to DK15844083.4T priority patent/DK3199512T3/da
Priority to CA2966521A priority patent/CA2966521C/en
Priority to AU2015320134A priority patent/AU2015320134B2/en
Priority to US15/514,980 priority patent/US10464870B2/en
Priority to PL15844083T priority patent/PL3199512T3/pl
Priority to KR1020177011661A priority patent/KR102601107B1/ko
Priority to RU2017114557A priority patent/RU2698724C2/ru
Priority to SI201531120T priority patent/SI3199512T1/sl
Priority to ES15844083T priority patent/ES2779549T3/es
Priority to EA201790727A priority patent/EA035720B1/ru
Priority to EP15844083.4A priority patent/EP3199512B1/en
Publication of WO2016045583A1 publication Critical patent/WO2016045583A1/zh
Priority to ZA201702942A priority patent/ZA201702942B/en
Priority to US16/534,352 priority patent/US11104629B2/en
Priority to HRP20200358TT priority patent/HRP20200358T1/hr
Priority to AU2020204171A priority patent/AU2020204171B2/en
Priority to US17/387,123 priority patent/US11746074B2/en
Priority to US18/460,864 priority patent/US20230406791A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J37/04—Mixing
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/202—Ethylene glycol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
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    • B01J2208/00539—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0081—Preparation by melting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for preparing a glycol.
  • ethylene glycol As an important monomer for bottle-grade polyester and fiber-grade polyester, ethylene glycol has a large application market. Propylene glycol is widely used in the food, pharmaceutical and cosmetic industries. For a long time, the production of glycols such as ethylene glycol and propylene glycol has been mainly obtained by using a petroleum-based olefin as a raw material through a two-step oxidation and hydration method. However, with the gradual depletion of petroleum resources, the use of renewable raw materials to prepare glycols has great commercial prospects.
  • the prior art discloses a process for preparing ethylene glycol by one-step catalytic hydrocracking using soluble sugar as a raw material.
  • the process is simple, the source of raw materials is rich, and the prospect of large-scale, commercial production.
  • low raw material sugar concentration such as WO2013015955A, CN102020531A
  • use of precious metals or a combination of precious metals and inexpensive metals as catalysts such as US4496780A, CN102643165A, CN103420797A
  • low ethylene yield such as US4496780A, CN102731259A, CN103420787A, CN101735014A, CN101613253A
  • CN103667365A etc.
  • CN102190562A and CN101735014A use a composite catalyst formed of a compound of tungsten and an active component, a monosaccharide dissolved in water such as 1% glucose as a raw material, and a yield of ethylene glycol of 30-45%.
  • CN103420796A uses a Ru/C and tungstic acid composite catalyst, a monosaccharide dissolved in water such as 1% glucose as a raw material, and a catalyst is used in a batch cycle, and the yield of ethylene glycol is 52-57%.
  • CN102731258A uses a Ni-W 2 C/AC supported catalyst, 18% glucose as a raw material, and the yield of the glycol is 50-60%, wherein the yield of ethylene glycol is 55%.
  • the yield of ethylene glycol of these applications is good, but due to the low concentration of the raw material sugar, there are the following disadvantages: First, the glucose concentration is 1-18%, the reaction system contains a large amount of water, and the boiling point ratio of ethylene glycol The water is high at 197.3 ° C. When rectifying and separating, the system first consumes a large amount of heat to distill off the water, resulting in high separation cost and uneconomical production.
  • the commonly used catalysts are inexpensive metals such as nickel and precious metals.
  • nickel-containing catalyst when used as a catalyst, when the acidity of the reaction system increases due to a hydrolysis side reaction of the raw material sugar, nickel reacts to release hydrogen gas and generate nickel ions Ni 2+ , causing the nickel-containing catalyst to slowly dissolve and lose hydrogenation. active. It has been reported in the literature that the pH of the reaction system can be adjusted to be above 7 to maintain the stability of the nickel-containing catalyst (CN103667365A).
  • Li Yan et al found that under the acidic condition of pH ⁇ 5, the raw sugar was in a relatively stable state, and there was no hydrolysis side reaction (Li Yan, Shen Shenqiu, etc., research on the mechanism of sucrose decomposition in non-pure sugar liquid, China beet sugar industry, 1996(2): 11-16), thus, the sugar hydrocracking system can increase the yield of glycol when it is operated under acidic conditions.
  • a noble metal such as Ru, Pt or the like
  • it can be stably present under a low pH condition, but the production cost of the glycol is greatly increased.
  • a carrier having a high specific surface area is selected to fix and disperse it.
  • Commonly used carriers such as alumina, silica, magnesia and other inorganic oxides, which are unstable under acidic conditions, are prone to neutralization reaction and dissolve in the reaction system, resulting in a decrease in the yield of the polyol (CN103159587A), and Activated carbon (CN103420796A, CN102643165A, CN102731258A, CN101613253A), which is easily methanated by hydrogenation under high temperature and hydrogen conditions.
  • the diol is produced at a lower cost by using an acid-resistant, inexpensive, and stable catalyst.
  • the present invention uses an acid-resistant, inexpensive, stable alloy which does not require a carrier as a main catalyst to prepare a glycol.
  • a method for preparing a glycol which comprises using sugar and hydrogen as raw materials to prepare a glycol in contact with a catalyst in water, wherein the catalyst used is a composite catalyst, and the composite catalyst is composed of a main catalyst and a cocatalyst.
  • the main catalyst is an acid-resistant alloy that is insoluble in water
  • the cocatalyst is a soluble tungstate and/or an insoluble tungsten compound.
  • the glycol is ethylene glycol.
  • the invention adopts an acid-resistant, inexpensive, stable, water-insoluble acid-proof alloy which does not require a carrier as a main catalyst, and is used as a composite catalyst to catalyze a sugar in combination with a cocatalyst of a soluble tungstate and/or an insoluble tungsten compound.
  • the diol is obtained, and the yield of the diol, especially ethylene glycol, can be guaranteed at a low production cost.
  • the water-insoluble acid-resistant alloy of the present invention is stable under acidic conditions, and it is not necessary to add a base to the reaction system to neutralize the acid produced by the hydrolysis of sugar.
  • the use of such an acid-resistant alloy procatalyst is particularly important for controlling the long-term, stable operation and production costs of the system when applying the process of the present invention to industrial continuous production.
  • the pH of the reaction system is from 1 to 7; more preferably, the pH of the reaction system is from 3 to 6.
  • the pH value of the system ⁇ 7 not only the hydrolysis side reaction of the raw material sugar during the reaction process can be avoided, the consumption of raw sugar in the ethylene glycol production is reduced, and the service life of the catalyst is ensured, and the use cost of the catalyst can be reduced.
  • the stability of the reaction system for long-term continuous operation is ensured, and the yield of ethylene glycol is high, and the yield of organic acid and polymer is low.
  • an organic or inorganic acid such as lactic acid, formic acid or acetic acid may be added to the system to adjust the pH of the reaction system.
  • an organic acid or a mineral acid is added together with the raw material sugar.
  • the sugar is selected from the group consisting of five carbon monosaccharides, disaccharides and oligosaccharides, six carbon monosaccharides, disaccharides and oligosaccharides, One or more of a soluble five-carbon polysaccharide, and a soluble six-carbon polysaccharide.
  • the original sources of raw sugar include, but are not limited to, sugar-based materials such as sugar beets, sugar cane, etc., starch-based materials such as corn, wheat, barley, cassava, etc., lignocellulosic based materials such as corn stover, corn cob, straw, bagasse, wood Etc., industrial residues of cellulose such as corncob slag, or polysaccharide materials including seaweed.
  • sugar-based materials such as sugar beets, sugar cane, etc.
  • starch-based materials such as corn, wheat, barley, cassava, etc.
  • lignocellulosic based materials such as corn stover, corn cob, straw, bagasse, wood Etc.
  • industrial residues of cellulose such as corncob slag, or polysaccharide materials including seaweed.
  • the soluble five-carbon polysaccharide and the soluble six-carbon polysaccharide refer to a five-carbon polysaccharide and a six-carbon polysaccharide which are soluble under the reaction conditions of the present invention, and not only the five-carbon polysaccharide and the six-carbon polysaccharide which are soluble at normal temperature.
  • the sugar is reacted with hydrogen in the form of an aqueous sugar solution (abbreviated as a sugar liquid), and the aqueous sugar solution has a concentration of 5 to 60% by weight. More preferably, it is 20-50% by weight.
  • a sugar liquid can be continuously fed through a transfer pump.
  • the invention adopts a suitable catalyst to make the reaction system have a small restriction on the concentration of the raw sugar, and can adopt a high concentration sugar liquid as a raw material, which greatly reduces the production cost of the glycol, especially the ethylene glycol, and realizes a large-scale and economical operation. Production of glycols.
  • the acid-resistant alloy comprises nickel, one or more rare earth elements, tin and aluminum; and each component is preferably 10-90 parts, 1-5 parts, 1-60 parts and 5-- by weight, respectively. 9 copies.
  • the rare earth element refers to a general term for 17 chemical elements having an atomic number of 21, 39, and 57-71 in the group IIIB of the periodic system, including lanthanum (La), cerium (Ce), cerium (Sm), and the like.
  • the acid-resistant alloy comprises nickel, one or more rare earth elements, tin, aluminum and tungsten; each component is preferably 10-90 parts, 1-5 parts, 1-60 parts by weight, respectively. , 5-9 parts and 1-90 parts.
  • the acid-resistant alloy comprises nickel, one or more rare earth elements, tin, aluminum, tungsten and molybdenum, and the components are preferably 10-90 parts, 1-5 parts, respectively, in parts by weight. 60 parts, 5-9 parts, 1-90 parts, and 0.5-20 parts.
  • the acid-resistant alloy comprises nickel, one or more rare earth elements, tin, aluminum, tungsten, molybdenum, and boron or phosphorus, and each component is preferably 10-90 parts by weight, respectively, in terms of parts by weight. 5 parts, 1-60 parts, 5-9 parts, 1-90 parts, 0.5-20 parts, and 0.01-5 parts.
  • the soluble tungstate is one or more of ammonium tungstate, sodium tungstate, sodium phosphotungstate; the insoluble tungsten compound is tungsten trioxide and/or tungstic acid.
  • the main catalyst is mixed with water and added to the reactor.
  • the amount of the main catalyst is from 0.01 to 10 times the amount of sugar fed per hour.
  • the reaction is in a continuous mode.
  • the amount of the main catalyst to be replenished is: 0.01 kg of the main catalyst added per 1000 kg of sugar.
  • Catalyst replenishment can be accomplished by discharging a portion of the old catalyst through a catalyst discharge valve (typically at the bottom of the reactor) and then replenishing the same amount of new catalyst through a catalyst feed valve (typically at the bottom of the reactor).
  • the soluble cocatalyst can be added to the sugar liquor first and then added to the reactor.
  • the soluble cocatalyst is used in an amount of from 0.01 to 5% by weight of the aqueous sugar solution. More preferably, it is 0.01 to 2% by weight. Most preferably, it is from 0.01 to 1% by weight.
  • the insoluble cocatalyst can be added to the reactor along with the main catalyst.
  • the amount of the insoluble cocatalyst is from 0.5 to 50% by weight of the main catalyst. More preferably, it is 5-20% by weight.
  • the reaction pressure of the reaction system is 5-12 MPa
  • the reaction temperature is 150-260 ° C
  • the reaction time is ⁇ 10 min.
  • the reaction pressure of the reaction system is 6-10 MPa
  • the reaction temperature is 180-250 ° C
  • the reaction time is 0.5-3 h.
  • the reaction time is most preferably from 0.5 to 2 hours.
  • the reaction is carried out in a slurry bed reactor.
  • the total volume of the formed reaction liquid does not exceed 80% of the reactor volume.
  • the slurry bed reactor is provided with a filter for retaining the insoluble portion of the catalyst in the reactor without being carried away by the gas and reaction liquid flowing out through the filter.
  • the main catalyst Before the start of the reaction, the main catalyst is added to the slurry bed reactor, and the hydrogen and the sugar liquid are simultaneously added to the reactor by a pump to carry out the reaction; the addition of the sugar and the main catalyst is in a continuous flow state, and the reaction liquid is discharged from the reactor. Continuous outflow.
  • the cocatalyst when it is a soluble tungsten compound, is fed to the reactor together with the sugar liquid; when it is an insoluble tungsten compound, it is fed to the reactor simultaneously with the main catalyst.
  • a filter is installed in the reactor. The filter can trap the catalyst, but the gas and the reaction liquid will continuously flow out through the filter and enter the condenser for gas-liquid separation.
  • the crude hydrogen is purified to remove CO, CO 2 , CH 4 , etc., and is again purified hydrogen and returned to the reactor.
  • the effluent flowing from the condenser enters the separation system, and water, ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol, and a cocatalyst are separated.
  • Products such as ethylene glycol, propylene glycol and butylene glycol can be purified by prior art techniques such as rectification. Water, sorbitol, glycerol, and a co-solvent that has been dissolved in the reaction system are returned to the reactor for recycling.
  • the catalyst of the present invention is inexpensive, stable, and does not require a carrier.
  • the invention can select a high concentration of sugar liquid as a raw material, and the production cost of the glycol, especially ethylene glycol, is low.
  • the yield of ethylene glycol of the process of the invention is high.
  • Figure 1 is a schematic flow diagram of the method of the present invention.
  • Figure 2 is a graph showing the change in ethylene glycol yield over time in Example 2.
  • Figure 1 is a schematic flow diagram of the method of the present invention.
  • the acid-resistant alloy main catalyst of the present invention can be directly prepared by a chemical reduction method or an electrolytic deposition method to obtain an active metal powder having a high specific surface area, or a metal alloy is first formed by a smelting method, and then a metal powder is formed by a mechanical pulverization method, an atomization method, or the like. Finally, a conventional Raney nickel catalyst activation method is used to form the active metal powder.
  • nickel, rare earth element, tin, aluminum, tungsten, molybdenum, and boron or phosphorus are 10-90 parts, 1-5 parts, 1-60 parts, 5-9 parts, 1-90 by weight, respectively.
  • Parts, 0.5-20 parts, and 0.01-5 parts are added to the melting furnace, and the temperature is raised to 1500-2000 ° C, and then the temperature is lowered, and the mixture is sufficiently mechanically stirred and then discharged to obtain a metal alloy.
  • the metal alloy was pulverized into a metal powder by a hammer mill, and the metal powder was immersed in a 20 wt% to 25 wt% aqueous sodium hydroxide solution at 70 to 95 ° C for 1-2 hours to form an active metal powder having a high specific surface area.
  • the acid-resistant alloy catalyst Ni80La1Sn30Al5 was prepared separately (indicating that the composition of the acid-resistant alloy was Ni80 parts + La1 parts + Sn30 parts + Al5 parts, the same below), the acid-resistant alloy catalyst Ni10Sm5Sn3Al9W70Mo5, the acid-resistant alloy catalyst Ni70Ce1Sn50Al7W5Mo1B5, the acid-resistant alloy catalyst Ni90Ce3Sn60Al9W20Mo5B1, and the acid resistance Alloy main catalyst Ni10Sm5Sn10Al9W90, acid-resistant alloy main catalyst Ni90Ce3Sn60Al9W20Mo20P0.01, acid-resistant alloy main catalyst Ni80La1Ce0.5Sn30Al5.
  • Acetic acid was added to the reaction vessel to bring the pH of the reaction system to 3.5.
  • the reaction solution and hydrogen after the reaction flowed out of the reaction vessel through the filter into the condensation tank, and the discharge rate of the reaction liquid was 3 L/h.
  • the effluent enters the rectification separation system to obtain water, ethylene glycol, propylene glycol, glycerol and sorbitol, and sodium tungstate, respectively, wherein the undistilled recombination includes glycerol and sorbitol and sodium tungstate to return to the reaction system for circulation.
  • the bottom of the condensation tank was sampled and its composition was determined by high performance liquid chromatography.
  • High performance liquid chromatography can be performed using conventional techniques.
  • the present invention provides the following experimental parameters for reference:
  • glucose conversion rate was 100%; yield of glycol was 77%, wherein ethylene glycol yield was 71%, propylene glycol yield was 7%, butanediol yield was 3%; methanol and ethanol The yield was 5%, and the other yield was 14%.
  • Figure 2 is a graph showing the change in the yield of ethylene glycol as a function of the operating time of the reaction system. As can be seen from the figure, the yield of ethylene glycol is kept substantially at about 70%. This indicates that the composite catalyst of the present invention can ensure that the yield of ethylene glycol is still stable after 500 hours of continuous operation of the reaction system.
  • the pH of the reaction system was changed to 9. The result was: glucose conversion was 100%; the yield of glycol was 68%, wherein the yield of ethylene glycol was 38%, the yield of propylene glycol was 27%, and the yield of butanediol was The rate was 3%; the yield of methanol and ethanol was 5%, and the other yield was 27%.
  • the acid-resistant alloy main catalyst was Ni10Sm5Sn3Al9W70Mo5, and the addition amount was 5000 g.
  • the feed composition was: 15 wt% glucose, 0.01 wt% ammonium tungstate, 84.9 wt% water, and the sugar liquid had a density of about 1.06 g/cm 3 .
  • glucose conversion rate was 100%; glycol yield was 66%, wherein ethylene glycol yield was 61%, propylene glycol yield was 3%, butanediol yield was 2%; methanol and ethanol The yield was 9%, and the other yield was 25%.
  • the acid-resistant alloy main catalyst was Ni70Ce1Sn50Al7W5Mo1B5, and the addition amount was 500 g.
  • the tungsten trioxide was added in an amount of 100 g.
  • the feed composition was: 40 wt% glucose, 60 wt% water, and the sugar liquid had a density of about 1.18 g/cm 3 .
  • the acid-resistant alloy main catalyst was Ni90Ce3Sn60Al9W20Mo5B1, and the addition amount was 1000 g.
  • Feed composition was: 15wt% xylose, 40wt% glucose, 1wt% malt disaccharide, 1wt% maltotriose, 1wt% sodium phosphotungstate, 42wt% water, sugar in a density of about 1.22g / cm 3.
  • the acid-resistant alloy main catalyst was Ni90Ce3Sn60Al9W20Mo5B1, and the addition amount was 5000 g.
  • the feed composition was: 50 wt% xylose, 0.1 wt% sodium tungstate, 49.9 wt% water, and the sugar liquid had a density of about 1.21 g/cm 3 .
  • the acid-resistant alloy main catalyst is Ni10Sm5Sn10Al9W90, and the added amount is 180g;
  • the feed composition was: 60 wt% glucose, 2 wt% sodium tungstate, 38 wt% water, and the sugar liquid had a density of about 1.29 g/cm 3 .
  • the reaction pressure was 12 MPa, and the reaction temperature was 260 °C.
  • glucose conversion rate was 100%; yield of glycol was 75%, wherein ethylene glycol yield was 65%, propylene glycol yield was 7%, butanediol yield was 3%; methanol and ethanol The yield was 11%, and the other yield was 14%.
  • the acid-resistant alloy main catalyst is Ni90Ce3Sn60Al9W20Mo20P0.01, and the added amount is 5g;
  • the feed composition was: 5 wt% glucose, 0.05 wt% sodium tungstate, 94.95 wt% water, and the sugar liquid had a density of about 1.02 g/cm 3 .
  • the reaction pressure was 6 MPa, and the reaction temperature was 180 °C.
  • the acid-resistant alloy main catalyst was Ni70Sm1Sn10Al7W5Mo0.5, and the addition amount was 1500 g.
  • the feed composition was: 40 wt% glucose, 60 wt% water, 0.5 wt% sodium tungstate, and the sugar liquid had a density of about 1.18 g/cm 3 .
  • glucose conversion rate was 100%; yield of glycol was 87%, wherein ethylene glycol yield was 80%, propylene glycol yield was 5%, butanediol yield was 2%; methanol and ethanol The yield was 3%, and the other yield was 10%.

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Abstract

提供了一种制备二元醇的方法，该方法以糖和氢气为原料，在水中与催化剂接触制备二元醇，所采用的催化剂为复合催化剂，所述复合催化剂由主催化剂和助催化剂组成，其中，所述主催化剂为不溶于水的耐酸合金；所述助催化剂为可溶性钨酸盐和/或不可溶性钨化合物。该方法采用耐酸的、廉价的、稳定的不需要载体的合金为主催化剂，能在生产成本较低情况下保证二元醇的高收率。

Description

一种制备二元醇的方法 技术领域
本发明涉及一种制备二元醇的方法。
背景技术
乙二醇作为瓶级聚酯和纤维级聚酯的重要单体，具有很大的应用市场。丙二醇可广泛应用于食品、医药和化妆品工业中。长期以来，乙二醇、丙二醇等二元醇的生产主要是以石油基烯烃为原料，经过氧化和水合二步法等方法得到。但随着石油资源的逐渐枯竭，利用可再生原料来制备二元醇具有巨大的商业前景。
现有技术中公开了使用可溶性糖为原料，经一步法催化加氢裂解来制备乙二醇的工艺。该工艺简单，原料来源丰富，具有大规模、商业化生产的前景。但是该工艺还存在各种不足。例如，原料糖浓度低(如WO2013015955A，CN102020531A)、使用贵金属或贵金属与廉价金属的组合作为催化剂(如US4496780A，CN102643165A，CN103420797A)、乙二醇得率低(如US4496780A，CN102731259A，CN103420787A，CN101735014A，CN101613253A，CN103667365A)等等而导致乙二醇的生产成本过高、催化剂活性不稳定、不能连续生产。
研究发现，在可溶性糖一步法催化加氢裂解制备二元醇的工艺中，在高温水相条件下原料糖极易发生水解等副反应而生成小分子物质，如乙酸、乳酸、蚁酸、呋喃、醛类、醇类等，进而导致体系的酸度增加(Sevilla M,Fuertes A B.Chemical and structural properties of carbonaceous products obtained byhydrothermal carbonization of saccharides.Chemistry-A European Journal.2009,15(16):4195-4203.)。同时，生成的醛、醇等进一步缩聚成的聚合物会堵塞催化剂孔道，会降低催化剂的催化活性、使用寿命、选择性和反应系统的长期运行稳定性，使得该工艺的经济可行性差，不能大规模、连续化的生产。同时，副产物的生成也导致了二元醇得率的下降。在现有专利申请中有公开原料糖中的40-60％会发生水解副反应(US5107018，CN101781167A，CN101781171A，CN101781166A)。
由于原料糖的浓度高时，其在高温水相条件下时，一是更易发生聚合而 堵住催化剂通道，导致催化剂的寿命降低，二元醇的生产成本增加，并因此对催化剂的催化活性要求更高以便在原料糖发生聚合之前将其加氢裂解。二是更易生成更高浓度的酸，并因此对催化剂的耐酸性要求更高。因此，现有专利申请中多是采用低浓度的糖为原料。例如，CN102190562A和CN101735014A采用钨的化合物与活性组分形成的复合催化剂，1％葡萄糖等溶于水的单糖为原料，乙二醇的收率为30-45％。CN103420796A采用Ru/C和钨酸复合催化剂，1％葡萄糖等溶于水的单糖为原料，间歇式循环使用催化剂，乙二醇的收率为52-57％。CN102731258A采用Ni-W2C/AC负载型催化剂，18％葡萄糖为原料，二元醇的收率为50-60％，其中乙二醇的收率为55％。这些申请的乙二醇的收率较好，但由于采用原料糖的浓度低，存在以下缺点：一是，葡萄糖浓度为1-18％，反应体系中含有大量水，而乙二醇的沸点比水高，为197.3℃，在进行精馏分离时，体系首先要消耗大量的热来将水蒸馏掉，导致分离成本高，生产不经济。二是这些申请均使用活性炭为载体，活性炭在高温、氢气条件下容易发生加氢反应而被甲烷化(US2002/0169344)。现有专利申请中CN102643165A公开了采用40-60％葡萄糖为原料，二元醇的收率为50-60％；但该申请是采用以活性炭为载体的Ru/C为催化剂；贵金属作为催化剂会使生产成本高，而活性炭存在甲烷化的风险，另外该申请的连续运行稳定性未知。
在可溶性糖一步法催化加氢裂解制备二元醇的工艺中，常用的催化剂有廉价金属(如镍)和贵金属。使用含镍催化剂为催化剂时，当反应体系的酸度由于原料糖发生水解副反应而增加时，镍会发生反应，释放出氢气并产生镍离子Ni2+，造成含镍催化剂缓慢溶解，失去加氢活性。有文献报道，可调节反应体系pH值在7以上来维持含镍催化剂的稳定性(CN103667365A)。在高pH值条件下，丙二醇的得率会大幅度增加而乙二醇的得率会大幅度降低(US5107018，CN101781167A，CN101781171A，CN101781166A)，同时水解副反应产生的酸如甲酸，乙酸，乳酸等会增多，总二元醇的得率也会降低(CN101544537A)。李雁等发现在pH<5的酸性条件下，原料糖处于较稳定的状态，基本不发生水解副反应(李雁，沈参秋等，非纯糖液中蔗糖分解机理的研究，中国甜菜糖业，1996(2)：11-16)，因而，糖加氢裂解体系在酸性条件下运行时可以提高二元醇的得率。使用贵金属，如Ru，Pt等，为催化剂时，其在低pH值条件下能稳定存在，但会大幅度增加二元醇的生产成本。为了降低贵金属的使用量并提高其催化活性，人们选择高比表面积的载体对其进行固定和分散。常用的载体如氧化铝，氧化硅，氧化镁等无机氧化物， 其在酸性条件下不稳定，容易发生中和反应而溶解在反应体系中，导致多元醇的收率降低(CN103159587A)，又如活性炭(CN103420796A，CN102643165A，CN102731258A，CN101613253A)，其在高温、氢气条件下容易发生加氢反应而被甲烷化。
综上所述，需要一种新的制备二元醇的方法。通过选用耐酸、廉价、稳定的催化剂，来以较低成本生产得到二元醇。
发明内容
本发明的目的是提供一种制备二元醇的方法。本发明采用耐酸的、廉价的、稳定的不需要载体的合金为主催化剂来制备二元醇。
本发明采用下述技术方案：
一种制备二元醇的方法，该方法以糖和氢气为原料，在水中与催化剂接触制备二元醇，所采用的催化剂为复合催化剂，所述复合催化剂由主催化剂和助催化剂组成，
其中，
所述主催化剂为不溶于水的耐酸合金；
所述助催化剂为可溶性钨酸盐和/或不可溶性钨化合物。
优选地，所述二元醇为乙二醇。
本发明采用耐酸的、廉价的、稳定的、不需要载体的不溶于水的耐酸合金作为主催化剂，与可溶性钨酸盐和/或不可溶性钨化合物的助催化剂配合使用来作为复合催化剂催化糖来制得二元醇，能在生产成本较低情况下保证二元醇尤其是乙二醇的收率。本发明的不溶于水的耐酸合金在酸性条件下是稳定的，无需在反应体系加入碱来中和糖水解产生的酸。在将本发明的方法应用到工业连续化生产中时，使用这种耐酸合金主催化剂对系统长期、稳定的运行和生产成本的控制尤为重要。
优选地，以上述方法制备乙二醇时，反应体系pH值为1-7；更优选地，反应体系pH值为3-6。通过控制体系pH值＜7，不但能避免原料糖在反应过程中发生水解副反应，降低了乙二醇生产中原料糖的消耗量，而且确保了催化剂的使用寿命，可以降低催化剂的使用成本，保证反应系统长期连续运行的稳定性，同时乙二醇的收率高，有机酸和聚合物的产量低。如果反应过程中产生的酸不足以维持低pH值，可向体系中添加乳酸、甲酸、乙酸等有机酸或无机酸来调节反应体系的pH值。通常，有机酸或无机酸随原料糖一起加入。
优选地，所述糖选自五碳单糖、二糖和寡糖，六碳单糖、二糖和寡糖， 可溶性的五碳多糖、和可溶性的六碳多糖中的一种或几种。原料糖的最初来源包括但不仅限于糖基物质如甜菜，甘蔗等，淀粉基物质如玉米，小麦，大麦，木薯等，木质纤维素基物质如玉米秸秆，玉米芯，麦杆，甘蔗渣，木材等，纤维素类的工业残渣如玉米芯渣等，或者多糖物质包括海藻等。本文中，可溶性的五碳多糖和可溶性的六碳多糖指在本发明的反应条件下可溶解的五碳多糖和六碳多糖，不仅仅指在常温下可溶解的五碳多糖和六碳多糖。
优选地，所述糖以糖水溶液(简称糖液)形式与氢气发生反应，糖水溶液浓度为5-60wt％。更优选地，为20-50wt％。在连续化操作中，糖液可通过输送泵来连续进料。本发明通过选用合适的催化剂使得反应体系对原料糖的浓度限制较小，能采用高浓度糖液为原料，这会大大降低二元醇尤其是乙二醇的生产成本，实现了大规模、经济的生产二元醇。
进一步地，所述耐酸合金包括镍、一种或多种稀土元素、锡和铝；各组分按重量份数计优选分别为10-90份、1-5份、1-60份和5-9份。
本文中，稀土元素指周期系ⅢB族中原子序数为21、39和57-71的17种化学元素的统称，包括镧(La)、铈(Ce)、钐(Sm)等。
更优选地，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝和钨；各组分按重量份数计优选分别为10-90份、1-5份、1-60份、5-9份和1-90份。
进一步优选地，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝、钨和钼，各组分按重量份数计优选分别为10-90份、1-5份、1-60份、5-9份、1-90份和0.5-20份。
最优选地，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝、钨、钼、和硼或磷，各组分按重量份数计优选分别为10-90份、1-5份、1-60份、5-9份、1-90份、0.5-20份、和0.01-5份。
优选地，所述可溶性钨酸盐为钨酸铵、钨酸钠、磷钨酸钠中的一种或几种；所述不可溶性钨化合物为三氧化钨和/或钨酸。
所述主催化剂与水混合后加入到反应器中。
优选地，所述主催化剂的用量为每小时糖进料量的0.01-10倍。
优选地，反应为连续模式。
优选地，所述主催化剂的补入量为：每进料1000kg糖，补入的主催化剂为0.01-5kg。催化剂的补入可以是通过催化剂出料阀(通常在反应器底部)排放出一部分旧的催化剂，然后通过催化剂进料阀(通常在反应器底部)补入相同量的新催化剂来实现。
所述可溶性助催化剂可先加入糖液中，之后一并加入反应器。优选地， 所述可溶性助催化剂的用量为糖水溶液的0.01-5wt％。更优选地，为0.01-2wt％。最优选地，为0.01-1wt％。
所述不可溶性助催化剂可与主催化剂一并加入反应器。优选地，所述不可溶性助催化剂的用量为主催化剂的0.5-50wt％。更优选地，为5-20wt％。
优选地，反应体系反应压力为5-12MPa，反应温度为150-260℃，反应时间≥10min。
更优选地，反应体系反应压力为6-10MPa，反应温度为180-250℃，反应时间0.5-3h。反应时间最优选为0.5-2小时。
优选地，所述反应在浆态床反应器中进行。为保证反应的顺利进行，形成的反应液的总体积不超过反应器容积的80％。
优选地，所述浆态床反应器中设有过滤器，用于将催化剂中的不可溶部分保留在反应器内，而不被经过滤器流出的气体和反应液带走。
反应开始前，向浆态床反应器中加入主催化剂，分别用泵将氢气和糖液同时加入反应器中，进行反应；糖和主催化剂的补入处于连续流动的状态，反应液从反应器中连续流出。对助催化剂，当其为可溶性钨化合物时，与糖液一起加入反应器中；当其为不可溶性钨化合物时，与主催化剂同时加入反应器中。反应器内装有过滤器。该过滤器可以截留催化剂，但气体和反应液会通过过滤器连续流出并进入冷凝器进行气液分离。粗氢气经净化脱除CO，CO2，CH4等，再次成为纯化氢气，返回反应器。从冷凝器流出的流出料进入分离系统，分离得到水、乙二醇、丙二醇、丁二醇、丙三醇、山梨醇和助催化剂等。利用现有技术(例如精馏)可纯化得到乙二醇、丙二醇和丁二醇等产品。水、山梨醇、丙三醇和已溶解在反应体系中的助催化剂返回反应器中循环反应。
本发明的有益效果如下：
1、本发明的催化剂廉价、稳定、不需要载体。
2、本发明可选用高浓度的糖液为原料，二元醇尤其是乙二醇的生产成本低。
3、本发明的方法的乙二醇的收率高。
附图说明
图1为本发明的方法的流程示意图。
图2为实施例2中乙二醇收率随时间变化图。
具体实施方式
下面结合附图及实施例对本发明进一步加以说明。
图1为本发明的方法的流程示意图。
实施例1
制备耐酸合金主催化剂：
本发明的耐酸合金主催化剂可采用化学还原法或者电解沉积法直接制备得到具有高比表面积的活性金属粉末，或者先采用熔炼法形成金属合金，然后采用机械粉碎法，雾化法等形成金属粉末，最后采用常规的雷尼镍催化剂活化方法形成活性金属粉末。例如，将镍、稀土元素、锡、铝、钨、钼、和硼或磷按重量份数计分别为10-90份、1-5份、1-60份、5-9份、1-90份、0.5-20份、和0.01-5份加入熔炼炉中，升温到1500-2000℃，之后降低温度，充分机械搅拌均匀后出炉，得到金属合金。采用锤式磨粉机将金属合金粉碎成金属粉末，用20wt％-25wt％氢氧化钠水溶液在70-95℃浸泡金属粉末1-2小时，形成具有高比表面积的活性金属粉末。
分别制备得到耐酸合金主催化剂Ni80La1Sn30Al5(表示耐酸合金的组成为Ni80份+La1份+Sn30份+Al5份，下同)、耐酸合金主催化剂Ni10Sm5Sn3Al9W70Mo5、耐酸合金主催化剂Ni70Ce1Sn50Al7W5Mo1B5、耐酸合金主催化剂Ni90Ce3Sn60Al9W20Mo5B1、耐酸合金主催化剂Ni10Sm5Sn10Al9W90、耐酸合金主催化剂Ni90Ce3Sn60Al9W20Mo20P0.01、耐酸合金主催化剂Ni80La1Ce0.5Sn30Al5。
实施例2
将6L水和1000g耐酸合金主催化剂Ni80La1Sn30Al5边搅拌边加入到10L反应釜中。将反应釜密封，常压下以1000L/h通入氢气置换反应釜内空气5小时后，将氢气压力升高到10MPa，继续通入氢气5小时，反应釜温度升到250℃，开始连续进料。进料组成为：50wt％葡萄糖，2wt％钨酸钠，48wt％水，糖液的密度约为1.23g/cm3；进料速度为3L/h。糖在反应釜内停留时间为2小时。在反应釜中加入乙酸使反应体系pH值为3.5。反应后的反应液和氢气通过过滤器流出反应釜进入冷凝罐，反应液的出料速度为3L/h，反应液经过冷却后从冷凝罐底部排出，得到流出液。流出液进入精馏分离系统，分别得到水、乙二醇、丙二醇、丙三醇和山梨醇以及钨酸钠，其中未被蒸馏出的重组份包括丙三醇和山梨醇以及钨酸钠返回反应系统循环反应。在冷凝罐底部取样，采用高效液相色谱检测其组成。
高效液相色谱检测采用常规技术即可。本发明提供以下实验参数供参考：
仪器：Waters 515HPLC Pump；
检测器：Water 2414 Refractive Index Detector；
色谱柱：300mm×7.8mm，Aminex HPX-87H离子交换柱；
流动相：5mmol/L硫酸溶液；
流动相流速：0.6ml/min；
柱温：60℃；
检测器温度：40℃。
结果为：葡萄糖转化率为100％；二元醇的收率为77％，其中，乙二醇收率为71％，丙二醇收率为7％，丁二醇收率为3％；甲醇和乙醇收率为5％，其它收率为14％。
图2为乙二醇收率随反应体系运行时间的变化图。从图中可以看出，乙二醇的收率基本保持在70％左右。这说明，本发明的复合催化剂能保证反应体系连续运行500小时后，乙二醇的收率仍然稳定。
改变反应体系pH值为9，结果为：葡萄糖转化率为100％；二元醇的收率为68％，其中，乙二醇收率为38％，丙二醇收率为27％，丁二醇收率为3％；甲醇和乙醇收率为5％，其它收率为27％。
实施例3
耐酸合金主催化剂为Ni10Sm5Sn3Al9W70Mo5，添加量为5000g。
进料组成为：15wt％葡萄糖，0.01wt％钨酸铵，84.9wt％水，糖液的密度约为1.06g/cm3。
反应体系pH＝6。
其它操作条件同实施例2。
结果为：葡萄糖转化率为100％；二元醇的收率为66％，其中，乙二醇收率为61％，丙二醇收率为3％，丁二醇收率为2％；甲醇和乙醇收率为9％，其它收率为25％。
实施例4
耐酸合金主催化剂为Ni70Ce1Sn50Al7W5Mo1B5，添加量为500g。
三氧化钨为加入量100g。
进料组成为：40wt％葡萄糖，60wt％水，糖液的密度约为1.18g/cm3。
反应体系pH＝4.2。
其它操作条件同实施例2。
结果为：葡萄糖转化率为100％；二元醇的收率为70％，其中，乙二醇收率为67％，丙二醇收率为2％，丁二醇收率为1％；甲醇和乙醇收率为9％，其 它收率为21％。
实施例5
耐酸合金主催化剂为Ni90Ce3Sn60Al9W20Mo5B1，添加量为1000g。
进料组成为：15wt％木糖，40wt％葡萄糖，1wt％麦芽二糖，1wt％麦芽三糖，1wt％磷钨酸钠，42wt％水，糖液的密度约为1.22g/cm3。
反应体系pH＝4.8。
其它操作条件同实施例2。
结果为：木糖、葡萄糖、麦芽二糖和麦芽三糖的转化率为100％；二元醇的收率为75％，其中，乙二醇收率为60％，丙二醇收率为11％，丁二醇收率为4％；甲醇和乙醇收率为7％，其它收率为18％。催化剂运行500小时后，乙二醇收率仍然稳定。
实施例6
耐酸合金主催化剂为Ni90Ce3Sn60Al9W20Mo5B1，添加量为5000g。
进料组成为：50wt％木糖，0.1wt％钨酸钠，49.9wt％水，糖液的密度约为1.21g/cm3。
反应体系pH＝4.8。
其它操作条件同实施例2。
结果为：木糖的转化率为100％；二元醇的收率为67％，其中，乙二醇收率为49％，丙二醇收率为16％，丁二醇收率为2％；甲醇和乙醇收率为12％，其它收率为21％。催化剂运行500小时后，乙二醇收率仍然稳定。
实施例7
耐酸合金主催化剂为Ni10Sm5Sn10Al9W90，添加量为180g；
进料组成为：60wt％葡萄糖，2wt％钨酸钠，38wt％水，糖液的密度约为1.29g/cm3。
反应压力为12MPa，反应温度为260℃。
其它操作条件同实施例2。
结果为：葡萄糖转化率为100％；二元醇的收率为75％，其中，乙二醇收率为65％，丙二醇收率为7％，丁二醇收率为3％；甲醇和乙醇收率为11％，其它收率为14％。
实施例8
耐酸合金主催化剂为Ni90Ce3Sn60Al9W20Mo20P0.01，添加量为5g；
进料组成为：5wt％葡萄糖，0.05wt％钨酸钠，94.95wt％水，糖液的密度约为1.02g/cm3。
反应体系pH＝1。
反应压力为6MPa，反应温度为180℃。
其它操作条件同实施例2。
结果为：葡萄糖转化率为100％；二元醇的收率为65％，其中，乙二醇收率为53％，丙二醇收率为9％，丁二醇收率为3％；甲醇和乙醇收率为4％，其它收率为31％。
实施例9
耐酸合金主催化剂Ni80La1Ce0.5Sn30Al5；其它操作条件同实施例2。
结果与实施例2类似。
实施例10
耐酸合金主催化剂为Ni70Sm1Sn10Al7W5Mo0.5，添加量为1500g。
进料组成为：40wt％葡萄糖，60wt％水，0.5wt％钨酸钠，糖液的密度约为1.18g/cm3。
反应体系pH＝4.2。
其它操作条件同实施例2。
结果为：葡萄糖转化率为100％；二元醇的收率为87％，其中，乙二醇收率为80％，丙二醇收率为5％，丁二醇收率为2％；甲醇和乙醇收率为3％，其它收率为10％。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (28)

  1. 一种制备二元醇的方法，其特征在于，该方法以糖和氢气为原料，在水中与催化剂接触制备二元醇，所采用的催化剂为复合催化剂，所述复合催化剂由主催化剂和助催化剂组成，
    其中，
    所述主催化剂为不溶于水的耐酸合金；
    所述助催化剂为可溶性钨酸盐和/或不可溶性钨化合物。
  2. 根据权利要求1所述的制备二元醇的方法，其特征在于，所述二元醇为乙二醇。
  3. 根据权利要求2所述的制备二元醇的方法，其特征在于，反应体系的pH值为1-7；更优选地，反应体系的pH值为3-6。
  4. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述糖选自五碳单糖、二糖和寡糖，六碳单糖、二糖和寡糖，可溶性的五碳多糖、和可溶性的六碳多糖中的一种或几种。
  5. 根据权利要求4所述的制备二元醇的方法，其特征在于，所述可溶性的五碳多糖和可溶性的六碳多糖指在所述体系的反应条件下可溶解的五碳多糖和可溶解的六碳多糖。
  6. 根据权利要求4所述的制备二元醇的方法，其特征在于，所述糖的最初来源为糖基物质，淀粉基物质，木质纤维素基物质，纤维素类的工业残渣，或者多糖物质；更优选地，所述糖基物质包括甜菜，甘蔗；所述淀粉基物质包括玉米，小麦，大麦，木薯；所述木质纤维素基物质包括玉米秸秆，玉米芯，麦杆，甘蔗渣，木材；所述纤维素类的工业残渣包括玉米芯渣；所述多糖物质包括海藻。
  7. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述糖以糖水溶液形式与氢气发生反应，糖水溶液浓度为5-60wt％；更优选地，为20-50wt％。
  8. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述耐酸合金包括镍、一种或多种稀土元素、锡和铝。
  9. 根据权利要求8所述的制备二元醇的方法，其特征在于，所述耐酸合金，按重量份数计，包括10-90份镍、1-5份稀土元素、1-60份锡和5-9份铝。
  10. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝和钨。
  11. 根据权利要求10所述的制备二元醇的方法，其特征在于，所述耐酸合金，按重量份数计，包括10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝和1-90份钨。
  12. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝、钨和钼。
  13. 根据权利要求12所述的制备二元醇的方法，其特征在于，所述耐酸合金，按重量份数计，包括10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝、1-90份钨和0.5-20份钼。
  14. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述耐酸合金包括镍、一种或多种稀土元素、锡、铝、钨、钼、和硼或磷。
  15. 根据权利要求14所述的制备二元醇的方法，其特征在于，所述耐酸合金，按重量份数计，包括10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝、1-90份钨、0.5-20份钼、和0.01-5份硼或磷。
  16. 根据权利要求8-15任一所述的制备二元醇的方法，其特征在于，所述稀土元素指周期系ⅢB族中原子序数为21、39和57-71的17种化学元素的统称。
  17. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述可溶性钨酸盐为钨酸铵、钨酸钠、磷钨酸钠中的一种或几种。
  18. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述不可溶性钨化合物为三氧化钨和/或钨酸。
  19. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述主催化剂的用量为每小时糖进料量的0.01-10倍。
  20. 根据权利要求7所述的制备二元醇的方法，其特征在于，所述可溶性助催化剂的用量为糖水溶液的0.01-5wt％；更优选地，为0.01-2wt％；最优选地，为0.01-1wt％。
  21. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，所述不可溶性助催化剂的用量为主催化剂的0.5-50wt％；更优选地，为5-20wt％。
  22. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，反应体系反应压力为5-12MPa，反应温度为150-260℃，反应时间≥10min。
  23. 根据权利要求22所述的制备二元醇的方法，其特征在于，反应体系反应压力为6-10MPa，反应温度为180-250℃，反应时间0.5-3h，优选为0.5-2h。
  24. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，反应为连续模式。
  25. 根据权利要求24所述的制备二元醇的方法，其特征在于，主催化剂的补入量为：每进料1000kg糖，补入的主催化剂为0.01-5kg。
  26. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，已溶解在反应体系中的助催化剂从产物中分离后循环使用。
  27. 根据权利要求1或2所述的制备二元醇的方法，其特征在于，反应在浆态床反应器中进行。
  28. 根据权利要求27所述的制备二元醇的方法，其特征在于，所述浆态床反应器中设有过滤器，用于将催化剂中的不可溶部分保留在反应器内而不被经过滤器流出的气体和反应液带走。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190014071A (ko) * 2016-06-03 2019-02-11 아이오와 콘 프로모션 보드 알도헥소스-생성 탄수화물의 에틸렌 글리콜로의 매우 선택적인 전환을 위한 연속 공정
EP3245181B1 (en) 2015-01-13 2019-10-23 Avantium Knowledge Centre B.v. Continuous process for preparing ethylene glycol from a carbohydrate source

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105523890B (zh) 2014-09-28 2021-04-16 长春美禾科技发展有限公司 一种制备二元醇的方法
CN105521788B (zh) 2014-09-28 2020-10-27 长春美禾科技发展有限公司 一种耐酸合金催化剂
CN106694009B (zh) * 2015-11-12 2019-12-13 中国科学院大连化学物理研究所 合金催化剂用于碳水化合物催化制备低碳二元醇的方法
CN106349014B (zh) * 2016-08-23 2020-08-18 上海交通大学 利用乙酰丙酸酯制备1,4-戊二醇的方法
CA3043991A1 (en) * 2016-12-19 2018-06-28 Shell Internationale Research Maatschappij B.V. Method for stabilization of glucose feed in the production of glycols
CN109107581A (zh) * 2017-06-22 2019-01-01 长春美禾科技发展有限公司 一种耐酸合金催化剂
CN111918856A (zh) * 2017-12-01 2020-11-10 爱荷华谷类推广协会 糖高度选择性转化为丙二醇或丙二醇和乙二醇的混合物的连续方法
CN110026202A (zh) * 2019-05-21 2019-07-19 北京石油化工学院 甘油加氢催化剂、催化剂前驱体及其制备方法与应用
CN112090428A (zh) * 2019-06-18 2020-12-18 长春美禾科技发展有限公司 一种合金催化剂及其制备方法，相关设备和用途
BR112022005612A2 (pt) 2019-09-24 2022-07-19 Iowa Corn Promotion Board Processo contínuo
US11680031B2 (en) 2020-09-24 2023-06-20 T. EN Process Technology, Inc. Continuous processes for the selective conversion of aldohexose-yielding carbohydrate to ethylene glycol using low concentrations of retro-aldol catalyst
US11319269B2 (en) 2020-09-24 2022-05-03 Iowa Corn Promotion Board Continuous processes for the selective conversion of aldohexose-yielding carbohydrate to ethylene glycol using low concentrations of retro-aldol catalyst
CN117480234A (zh) * 2021-06-22 2024-01-30 雪佛龙美国公司 多金属本体加氢加工催化剂

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101735014A (zh) * 2008-11-26 2010-06-16 中国科学院大连化学物理研究所 一种多羟基化合物制乙二醇的方法
CN102190562A (zh) * 2010-03-17 2011-09-21 中国科学院大连化学物理研究所 一种多羟基化合物制乙二醇的方法
CN102731258A (zh) * 2012-05-21 2012-10-17 中国科学院大连化学物理研究所 一种碳水化合物内循环催化转化制备低碳多元醇的方法
CN103848720A (zh) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 一种制备乙二醇的方法

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496780A (en) 1983-06-22 1985-01-29 Uop Inc. Hydrocracking of polyols
DE3928285A1 (de) 1989-08-26 1991-02-28 Basf Ag Verfahren zur herstellung niederer, mehrwertiger alkohole
JP3293846B2 (ja) 1991-07-23 2002-06-17 日興リカ株式会社 触媒用球状ラネ−合金の製造方法
KR100375306B1 (ko) 2000-09-27 2003-03-10 한국통산주식회사 고강도 선재 및 판재용 구리(Ｃｕ)-니켈(Ｎｉ)-망간(Ｍｎ)-주석(Ｓｎ)-알루미늄(Ａｌ),실리콘(Ｓｉ)-세리움(Ｃｅ),란탄(Ｌａ), 니오디미움(Ｎｄ),프로메티움(Ｐｒ) 합금
US6900361B2 (en) 2001-05-08 2005-05-31 Battelle Memorial Institute Process for lactose conversion to polyols
US7663004B2 (en) * 2002-04-22 2010-02-16 The Curators Of The University Of Missouri Method of producing lower alcohols from glycerol
CN1683293A (zh) 2005-03-01 2005-10-19 大成多元醇投资有限公司 一种由山梨醇裂解生产二元醇和多元醇的方法
CN101199930A (zh) * 2006-12-14 2008-06-18 马波 一种高碳多元醇加氢裂解催化剂,其制备方法和应用
CN101544537A (zh) 2008-03-25 2009-09-30 西安航天华威化工生物工程有限公司 一种由c6糖醇生产低碳化工醇的方法
CN101613253B (zh) 2008-06-25 2012-10-24 中国科学院大连化学物理研究所 一种糖及糖醇的催化裂解方法
CN101781171A (zh) 2010-03-18 2010-07-21 西安近代化学研究所 二元醇的制备方法
CN101781166B (zh) 2010-03-18 2013-06-05 西安近代化学研究所 二元醇的制备方法
CN101781167B (zh) 2010-03-18 2013-04-17 西安近代化学研究所 二元醇和多元醇的合成方法
CN102020531A (zh) 2010-10-20 2011-04-20 华东理工大学 一种低碳多元醇的制备方法
US20120172588A1 (en) 2010-12-30 2012-07-05 Ming Qiao Catalytic biomass deconstruction
CN102675045B (zh) * 2011-03-15 2015-04-01 中国科学院大连化学物理研究所 一种糖溶液制备乙二醇、1,2-丙二醇的方法
CN102643165B (zh) 2011-06-28 2014-07-02 中国科学院大连化学物理研究所 连续加氢裂解糖转化生产乙二醇及1,2-丙二醇的方法
WO2013015955A2 (en) 2011-07-28 2013-01-31 Uop Llc Generation of polyols from saccharides
US20110312488A1 (en) * 2011-07-28 2011-12-22 Uop Llc Catalyst system for generation of polyols from saccharide containing feedstock
CN103159587A (zh) 2011-12-08 2013-06-19 中国科学院大连化学物理研究所 一种催化剂在生物多元醇加氢裂解中的应用
CN103420798B (zh) * 2012-05-18 2015-12-09 中国科学院大连化学物理研究所 一种高效催化转化纤维素类原料到二元醇的方法
CN103420796B (zh) 2012-05-21 2015-05-20 中国科学院大连化学物理研究所 一种高金属负载量催化剂用于碳水化合物制乙二醇的方法
CN103420787B (zh) 2012-05-21 2015-01-28 中国科学院大连化学物理研究所 近或超临界水条件下碳水化合物制小分子多元醇的方法
CN103420797B (zh) 2012-05-21 2015-04-08 中国科学院大连化学物理研究所 低金属负载量催化剂用于碳水化合物制备乙二醇的方法
CN102731259A (zh) 2012-06-26 2012-10-17 北京大学 Cu基负载型催化剂在高碳多元醇选择氢解制备低碳二元醇中的应用
CN103667365A (zh) 2012-08-31 2014-03-26 郸城财鑫糖业有限责任公司 一种农作物秸秆制备二元醇的方法
WO2015154258A1 (en) * 2014-04-09 2015-10-15 Petroliam Nasional Berhad (Petronas) Selective conversion of saccharide containing feedstock to ethylene glycol
DK3145902T3 (en) * 2014-05-19 2018-10-01 Iowa Corn Promotion Board PROCEDURE FOR CONTINUOUS PREPARATION OF ETHYLENGYLYCOL FROM CARBOHYDRATES
CN105523890B (zh) * 2014-09-28 2021-04-16 长春美禾科技发展有限公司 一种制备二元醇的方法
CN105521788B (zh) 2014-09-28 2020-10-27 长春美禾科技发展有限公司 一种耐酸合金催化剂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101735014A (zh) * 2008-11-26 2010-06-16 中国科学院大连化学物理研究所 一种多羟基化合物制乙二醇的方法
CN102190562A (zh) * 2010-03-17 2011-09-21 中国科学院大连化学物理研究所 一种多羟基化合物制乙二醇的方法
CN102731258A (zh) * 2012-05-21 2012-10-17 中国科学院大连化学物理研究所 一种碳水化合物内循环催化转化制备低碳多元醇的方法
CN103848720A (zh) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 一种制备乙二醇的方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3245181B1 (en) 2015-01-13 2019-10-23 Avantium Knowledge Centre B.v. Continuous process for preparing ethylene glycol from a carbohydrate source
KR20190014071A (ko) * 2016-06-03 2019-02-11 아이오와 콘 프로모션 보드 알도헥소스-생성 탄수화물의 에틸렌 글리콜로의 매우 선택적인 전환을 위한 연속 공정
JP2019519539A (ja) * 2016-06-03 2019-07-11 アイオワ・コーン・プロモーション・ボード アルドヘキソースを生じる炭水化物のエチレングリコールへの高度に選択的な変換のための連続プロセス
US10975010B2 (en) 2016-06-03 2021-04-13 Iowa Corn Promotion Board Continuous processes for the highly selective conversion of aldohexose-yielding carbohydrate to ethylene glycol
US10988426B2 (en) 2016-06-03 2021-04-27 Iowa Com Promotion Board Continuous processes for the highly selective conversion of aldohexose-yielding carbohydrate to ethylene glycol
TWI743130B (zh) * 2016-06-03 2021-10-21 愛荷華玉米推廣委員會 將產出醛己醣之碳水化合物高選擇性轉化為乙二醇之連續方法
JP2022071039A (ja) * 2016-06-03 2022-05-13 アイオワ・コーン・プロモーション・ボード アルドヘキソースを生じる炭水化物のエチレングリコールへの高度に選択的な変換のための連続プロセス
JP7094894B2 (ja) 2016-06-03 2022-07-04 アイオワ・コーン・プロモーション・ボード アルドヘキソースを生じる炭水化物のエチレングリコールへの高度に選択的な変換のための連続プロセス
KR102437548B1 (ko) * 2016-06-03 2022-08-26 아이오와 콘 프로모션 보드 알도헥소스-생성 탄수화물의 에틸렌 글리콜로의 매우 선택적인 전환을 위한 연속 공정

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