CN101830774A - Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials - Google Patents
Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials Download PDFInfo
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- CN101830774A CN101830774A CN 201010145030 CN201010145030A CN101830774A CN 101830774 A CN101830774 A CN 101830774A CN 201010145030 CN201010145030 CN 201010145030 CN 201010145030 A CN201010145030 A CN 201010145030A CN 101830774 A CN101830774 A CN 101830774A
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Abstract
The invention discloses a method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials, in particular to a method for preparing C2-4 dihydric alcohol and polyalcohol by directly hydrocracking glucose or sorbitol as a raw material. The method comprises the steps of: directly hydrocracking a nickel/aluminum catalyst, glucose or sorbitol water phase to generate a mixture of the C2-4 dihydric alcohol and the polyalcohol under the high-temperature and high-pressure conditions in an alkaline environment; and carrying out vacuum distillation and separation on a cracked product to obtain a single chemical alcohol product. The production method has the advantages of regenerated raw materials, simple and novel process, low cost, high yield and capabilities of completely replacing petroleum resources and producing various chemical alcohol products.
Description
Technical field
The present invention relates to a kind ofly prepare C by starchy material
2-4The method of dibasic alcohol and polyvalent alcohol, belong to chemical field, particularly with conventional corn starch be the glucose that makes of raw material or sorbyl alcohol in the presence of nickel/Al catalysts, the method for ethylene glycol, propylene glycol, glycerol and various butyleneglycol isomer is produced in the high-temperature and high-pressure hydrogenation cracking.
Background technology
Ethylene glycol, propylene glycol, glycerol and various butyleneglycol all are industrial important chemical material, be widely used in fields such as chemical industry, medicine, weaving, macromolecular material, the market application quantity is big, and only ethylene glycol China annual requirement is more than 600 ten thousand tons, and global annual requirement reaches more than 1,700 ten thousand tons.Petroleum is mainly used in the production of present industrial ethylene glycol, propylene glycol etc., produces ethene or propylene after the cracking, by epoxidation, generates ethylene glycol and propylene glycol.Along with the recovery of global economy, the rise of oil price, the price of polyvalent alcohol goes up gradually on the world market.If with starch is the basic organic chemical industry's product of raw material substitution oil production, for solving China's oil shortage of resources problem, save a large amount of foreign exchanges, carry out the strategy of sustainable development, quickening to advance modernization construction, there are great realistic significance and social effect in round Realization well-off society.
Chinese patent CN 1683293A discloses a kind of " being produced the method for dibasic alcohol and polyvalent alcohol by cracking sorbierite ", wherein mention under the condition that nickel/ruthenium catalyst exists, high-temperature and high-pressure hydrogenation cracking sorbyl alcohol generates products such as ethylene glycol, propylene glycol, butyleneglycol.The present invention is to be that the cracking of raw material direct hydrogenation makes ethylene glycol, propylene glycol, butyleneglycol etc., the cracking route reaction mild condition that this technology adopted, catalyzer novelty, processing condition uniqueness with glucose or sorbyl alcohol.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of by starchy material production C
2-4The method of dibasic alcohol and polyvalent alcohol, particularly with conventional corn starch be the glucose that makes of raw material or sorbyl alcohol in the presence of nickel/Al catalysts, the method for ethylene glycol, propylene glycol, glycerol and various butyleneglycol isomer is produced in the high-temperature and high-pressure hydrogenation cracking.
The object of the present invention is achieved like this:
A kind of starchy material prepares C
2-4The method of dibasic alcohol and polyvalent alcohol; : is the solution of 20-45% at aqueous phase with sorbyl alcohol or glucose weight proportion, adds liquid caustic soda, in the presence of nickel/Al catalysts, sorbyl alcohol or D/W High Temperature High Pressure hydrocracking is generated C
2-4Dibasic alcohol and polyvalent alcohol.
Described sorbitol aqueous solution hydrocracking temperature is 200-250 ℃, and optimum temps is 230 ℃; D/W hydrocracking temperature is 185-230 ℃, and optimum temps is 200 ℃.
Described sorbyl alcohol or D/W hydrocracking pressure are 11-13Mpa, optimum pressure 12Mpa.
Dry substance is 30%-45% in described sorbyl alcohol or the D/W.
Described sorbitol aqueous solution hydrocracking pH value is 11-13, and best pH value is 12, and D/W hydrocracking pH value is 8-11, and best pH value is 9.
The described sorbyl alcohol water hydrocracking reaction times is 30-60 minute, and Best Times is 60 minutes, and the G/W phase hydrogenation scission reaction time is 90-120 minute, and Best Times is 90 minutes.
Described dibasic alcohol is ethylene glycol, propylene glycol, various butyleneglycol isomer, and described polyvalent alcohol is a glycerol.
Described various butyleneglycol isomer is 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol.
The weight of mixture consists of after the cracking: ethylene glycol 20-30%, propylene glycol 40-60%, glycerol 3-6%, butyleneglycol isomer 5-10%, surplus materials account for 3-10%, and (first and second alcohol respectively account for 0.5-1%, and glucose or sorbyl alcohol account for 3-6%, organic acid salt 2-3%, other material 1-4%).
Described starchy material is sorbyl alcohol or glucose.
Beneficial effect: present invention resides in and adopt nickel/Al catalysts under the alkaline environment, the direct hydrogenation cracking under high-temperature and high-pressure conditions of glucose or sorbyl alcohol water generates C
2-4The mixture of dibasic alcohol and polyvalent alcohol, split product through rectification under vacuum separate single chemical industry alcohol product.The advantage of this production method is that raw material is renewable, and technology is simply novel, and cost is low, and the yield height can replace petroleum resources to produce multiple chemical industry alcohol product simultaneously fully.
Embodiment:
Embodiment 1
Scission reaction raw materials of glucose of the present invention can conventional corn starch be a raw material through liquefaction, saccharification, from step such as handing over, concentrate to make, and described sorbyl alcohol makes for the glucose hydrogenation.
Catalyzer of the present invention is nickel/Al catalysts, and hydrogen is that the content that makes after the absorption of water-gas process transformation is purified is 99.99% hydrogen.
Of the present invention by starchy material production C
2-4The method of dibasic alcohol and polyvalent alcohol comprises the steps:
(1) processing of raw material
With glucose with water and the sodium hydroxide that is used to adjust PH mix by a certain percentage: in order to reach reasonable lytic effect, the weight ratio of mixed glucose in water is about 30-45%, and PH is controlled at 8-11, and the best is 9; Or sorbyl alcohol is configured to the solution of 30-45% according to the method described above, and PH is controlled at 11-13, and the best is 12.
(2) heating
The raw material of handling is being heated to 170-180 ℃, is supplying with next step scission reaction and use;
(3) scission reaction
Glucose water scission reaction: controlled temperature is 180-230 ℃, and reaction pressure is 11-13Mpa, and pH value is 9, and the reaction times is 90-120 minute, controls the terminal point of reaction according to the effect of scission reaction, and the best reaction times is about 90 minutes; Sorbyl alcohol water scission reaction: controlled temperature is 200-250 ℃, and reaction pressure is 11-13Mpa, and pH value is 12, and the reaction times is 30-60 minute, controls the terminal point of reaction according to the effect of scission reaction, and the best reaction times is about 60 minutes.
(4) recovery of hydrogen, catalyzer
Reacted mixed solution reacts usefulness for next batch at the bottom of reactor bottom filtering system is stayed still with catalyzer, and then by gas-liquid separator, circulating hydrogen is through hydrogen pressure machine recycling again.Reaction mass is added continuously and discharging in still, and catalyzer remain in the still, owing to reduced the turnover material time, reaction efficiency is improved more than two times, can avoid catalyzer frequently to come in and go out simultaneously the valve that the hydrogenation still causes and wearing and tearing of catalyzer.
(5) mixture dewaters, takes off heavy constituent
Mixed solution is by dehydration tower, first ethanol tower, make moisture controlled in the mixed solution below 0.5%, by weight-removing column pressure be-0.085MPa again, isolate unreacted glucose or sorbyl alcohol and organic acid salt under temperature 175-200 ℃, the intact heavy constituent of these unreacteds come back to the raw material arrangement step and stock liquid reconfigures, and further carry out the high-pressure hydrogenation scission reaction.
(6) rectifying separation
Obtain comparatively purified C by dehydration, weight-removing column
2-4Dibasic alcohol and polyol blends successively enter and presort tower, the ethylene glycol tower, and 2,3-butyleneglycol tower, 1,2 ,-propylene glycol tower, 1,2-butyleneglycol tower etc. is progressively separated each component.
Concrete data are as follows:
| Sequence number | Title | Temperature ℃ | Pressure MPa |
| ??1 | The 1# dehydration tower | ??166 | ??0.56 |
| ??2 | The 2# dehydration tower | ??140 | ??0.21 |
| ??3 | The 3# dehydration tower | ??115 | ??0.03 |
| ??4 | The 2# dehydration tower | ??82 | ??-0.082 |
| ??5 | Dehydration tower again | ??147 | ??-0.078 |
| ??6 | The 1# weight-removing column | ??175 | ??-0.085 |
| ??7 | The 2# weight-removing column | ??200 | ??-0.099 |
| ??8 | Presort tower | ??162 | ??-0.078 |
| ??9 | 1,2 ,-propylene glycol tower | ??153 | ??-0.074 |
| ??10 | 2,3-butyleneglycol tower | ??146 | ??-0.078 |
| ??11 | The ethylene glycol tower | ??122 | ??-0.098 |
| ??12 | 1,2-butyleneglycol tower | ??162 | ??-0.075 |
| ??13 | The glycerol tower | ??180 | ??-0.09 |
| ??14 | The first ethanol tower | ??102 | ??0.015 |
| ??15 | Methanol column | ??80 | ??0.015 |
Embodiment 2
1. sorbyl alcohol hydrocarbon hydrocracking reaction
Sorbyl alcohol liquid thin up to 30% with 100Kg70%, mix with 20% sodium hydroxide, feed liquid is transferred to PH=12, and stock liquid is preheated to 170 ℃, enters reactor then, in the presence of nickel/Al catalysts, with hydrogen 230 ℃ of temperature, scission reaction takes place down in pressure 12MPa, reacts to obtain the 233Kg split product after 60 minutes, wherein contain ethylene glycol, propylene glycol, glycerol, various butyleneglycol isomer.Some unreacted sorbyl alcohols and organic acid salt come back to raw material arrangement step and stock liquid and reconfigure after rectifying tower takes off heavily, further carry out the high-pressure hydrogenation scission reaction.
2. rectifying separation
With above-mentioned split product through dehydration, take off heavy constituent the water in the mixture and heavy constituent such as formate, acetate, propionic salt, lactic acid salt etc. removed, carry out rectification under vacuum by a plurality of stuffing rectification columns then and separate, obtain single chemical industry alcohol product and methyl alcohol, ethanol byproducts.
Embodiment 3
1. glucose hydrocarbon hydrocracking reaction
Glucose Liquid thin up to 30% with 100Kg75%, mix with 20% sodium hydroxide, feed liquid is transferred to PH=9, and stock liquid is preheated to 170 ℃, enters reactor then, in the presence of nickel/Al catalysts, with hydrogen 200 ℃ of temperature, scission reaction takes place down in pressure 12MPa, reacts to obtain the 250Kg split product after 90 minutes, wherein contain ethylene glycol, propylene glycol, glycerol, various butyleneglycol isomer.Some unreacted glucose and organic acid salt come back to raw material arrangement step and stock liquid and reconfigure after rectifying tower takes off heavily, further carry out the high-pressure hydrogenation scission reaction.
2. rectifying separation
With above-mentioned split product through dehydration, take off heavy constituent the water in the mixture and heavy constituent such as formate, acetate, propionic salt, lactic acid salt etc. removed, carry out rectification under vacuum by a plurality of stuffing rectification columns then and separate, obtain single chemical industry alcohol product and methyl alcohol, ethanol byproducts.
More than implement only to be used to illustrate preferred implementation of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described field those of ordinary skill is possessed; any modification of being done within the spirit and principles in the present invention, be equal to and substitute and improvement etc., it all should be encompassed within the technical scheme scope that the present invention asks for protection.
Claims (10)
1. a starchy material prepares C
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: is the solution of 20-45% at aqueous phase with sorbyl alcohol or glucose weight proportion, adds liquid caustic soda, in the presence of nickel/Al catalysts, sorbyl alcohol or D/W High Temperature High Pressure hydrocracking is generated C
2-4Dibasic alcohol and polyvalent alcohol.
2. a kind of starchy material according to claim 1 prepares C
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described sorbitol aqueous solution hydrocracking temperature is 200-250 ℃, and optimum temps is 230 ℃; D/W hydrocracking temperature is 185-230 ℃, and optimum temps is 200 ℃.
3. a kind of starchy material according to claim 1 prepares C
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described sorbyl alcohol or D/W hydrocracking pressure are 11-13Mpa, optimum pressure 12Mpa.
4. a kind of starchy material according to claim 1 prepares C
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: dry substance is 30%-45% in described sorbyl alcohol or the D/W.
5. prepare C according to the described a kind of starchy material of claim
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described sorbitol aqueous solution hydrocracking pH value is 11-13, and best pH value is 12, and D/W hydrocracking pH value is 8-11, and best pH value is 9.
6. prepare C according to any described a kind of starchy material of claim 1-5
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: the described sorbyl alcohol water hydrocracking reaction times is 30-60 minute, and Best Times is 60 minutes, and the G/W phase hydrogenation scission reaction time is 90-120 minute, and Best Times is 90 minutes.
7. prepare C according to any described a kind of starchy material of claim 1-5
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described dibasic alcohol is ethylene glycol, propylene glycol, various butyleneglycol isomer, and described polyvalent alcohol is a glycerol.
8. a kind of starchy material according to claim 7 prepares C
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described various butyleneglycol isomer are 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol.
9. prepare C according to any described a kind of starchy material of claim 1-5
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: the weight of mixture consists of after the cracking:
Ethylene glycol 20-30%, propylene glycol 40-60%, glycerol 3-6%, butyleneglycol isomer 5-10%, surplus materials account for 3-10% (first and second alcohol respectively account for 0.5-1%, and glucose or sorbyl alcohol account for 3-6%, organic acid salt 2-3%, other material 1-4%).
10. prepare C according to any described a kind of starchy material of claim 1-5
2-4The method of dibasic alcohol and polyvalent alcohol is characterized in that: described starchy material is sorbyl alcohol or glucose.
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| CN 201010145030 CN101830774A (en) | 2010-04-13 | 2010-04-13 | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials |
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| CN 201010145030 CN101830774A (en) | 2010-04-13 | 2010-04-13 | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391066A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for carrying out one-step method to produce low-molecular-weight polyalcohols by utilizing glucose |
| CN102643165A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
| CN102643164A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose |
| CN102675045A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution |
| CN103687837A (en) * | 2011-07-28 | 2014-03-26 | 环球油品公司 | Continuous catalytic generation of polyols from cellulose |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
| CN101781166A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
-
2010
- 2010-04-13 CN CN 201010145030 patent/CN101830774A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
| CN101781166A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of the Chinese institute of Chemical Engineers》 19850131 Feng-Wen Chang et al. A Kinetic Study on the Hydrogenolysis of Sorbitol over Raney Nickel Catalysts 17-23 1-10 第16卷, 第1期 * |
| 《React. Kinet. Catal. Lett.》 19831231 D. K. Sohounloue et al. Catalytic Hydrogenolysis of Sorbitol 391-397 1-10 第22卷, 第3-4期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675045A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution |
| CN102643165A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
| CN102643164A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose |
| CN102643164B (en) * | 2011-06-28 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose |
| CN102643165B (en) * | 2011-06-28 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
| CN103687837A (en) * | 2011-07-28 | 2014-03-26 | 环球油品公司 | Continuous catalytic generation of polyols from cellulose |
| CN102391066A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for carrying out one-step method to produce low-molecular-weight polyalcohols by utilizing glucose |
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Application publication date: 20100915 |