CN101544537A - Method for producing low carbon chemical ethanol from C6 sugar alcohol - Google Patents
Method for producing low carbon chemical ethanol from C6 sugar alcohol Download PDFInfo
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- CN101544537A CN101544537A CN200810017788A CN200810017788A CN101544537A CN 101544537 A CN101544537 A CN 101544537A CN 200810017788 A CN200810017788 A CN 200810017788A CN 200810017788 A CN200810017788 A CN 200810017788A CN 101544537 A CN101544537 A CN 101544537A
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Abstract
The invention relates to a method for producing low carbon chemical ethanol from C6 sugar alcohol. Chinese patent disclosed number CN1683293A discloses a method for producing dihydric alcohol and andpolyhydric alcohol by cracking sorbierite. The method comprises the steps of converting the sorbierite into glycol, propanediol and glycerin, but process data and a process route as well as products do not achieve good industrial production requirements. The method mainly adopts a continuous process to hydrocrack the C6 sugar alcohol to generate a low carbon ethanol mixture and finally obtains a single (or mixed) product by separating and refining in alkaline environment, in the presence of a nickel chrome catalyst and at high temperature and high pressure. The process route has the advantages of simple process, easy operation, high yield in unit time and variety of the products; and as the catalyst has different selectivities, the composition rate of the produced products can be substantially adjusted.
Description
Technical field
The present invention relates to a kind of by C
6The cracking of sugar alcohol water is produced chemical industry alcohol and (is mainly C
2-4Dibasic alcohol) method, particularly making starch with cereal is that raw material makes C
6Sugar alcohol is produced C by its hydrocracking again
2-4The method of chemical industry alcohol.
Background technology
Along with the continuous development of science and technology, people are also increasingly sharpened to various chemical engineering industry consumptions of raw materials, and dibasic alcohol is as a type of industrial chemicals, and the demand in market is big especially.But the source of the dibasic alcohol on the market mainly relies on the oil purification processing to produce now, and oil under constantly using, inevitably progressively moves towards exhausted as a kind of Nonrenewable resources.And, by the dibasic alcohol (as propylene glycol, ethylene glycol) of oil production, the cost height, seriously polluted.In order to solve the source problem that comes of dibasic alcohol, people have invested sight in the agricultural-food of aboundresources, cheap, environmental protection.Grain constantly increases production in recent years, and whole world grain occurs superfluous, and grain deep processing industry is constantly developed, by the C of W-Gum production
6Sugar alcohol can obtain many dibasic alcohol (ethylene glycol, propylene glycol, butyleneglycol) and a spot of glycerol through hydrocracking.
Chinese patent publication number CN1683293A discloses " a kind of method of being produced dibasic alcohol and polyvalent alcohol by cracking sorbierite ", wherein mention the hydrogenation reaction in the presence of nickel/ruthenium catalyst, this reaction comprises sorbyl alcohol is changed into ethylene glycol, propylene glycol and glycerine, but its process data and operational path and product all do not reach good suitability for industrialized production requirement.
Summary of the invention
The object of the present invention is to provide the C of a kind of employing by nickel/palladium catalyst for cracking
6The method of chemical industry alcohol is given birth in the cracking of sugar alcohol water, particularly with cereal as being raw material production C with the corn
6Sugar alcohol is again with C
6The method of dibasic alcohol such as ethylene glycol, propylene glycol and various butyleneglycol isomer etc. is produced in the sugar alcohol cracking.
For achieving the above object, the technical solution used in the present invention is:
A kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, and its special character is: this method is included in alkaline condition and nickel/palladium catalyst for cracking exists down, at aqueous phase C
6The proportioning of sugar alcohol in the aqueous solution is 30-60%, and unit is: Wt/V; C
6The mol ratio of sugar alcohol and hydroxide ion is 3-14:1, with C
6The sugar alcohol hydrogenation cracking generates the mixture of polyvalent alcohol, obtains single or mixing prod behind separation and purification respectively.
Above-mentioned is 45% in the proportioning of aqueous phase sugar alcohol in the aqueous solution, and unit is: Wt/V; C
6The mol ratio of sugar alcohol and sodium hydroxide is 4:1.
Above-mentioned hydrocracking is 225-260 ℃ in temperature of reaction, and optimal temperature is 240 ℃, and reaction pressure is 10-15MPa, and optimum pressure is 12MPa.
The C of above-mentioned preparation
6The sugar alcohol solution pH value is 12-13.5, and the optimum pH value is 13; Reaction times is 40-60 minute, and the optimum time is 60 minutes.
Above-mentioned chemical industry alcohol is C
2-4Dibasic alcohol, dibasic alcohol are ethylene glycol, propylene glycol and various butyleneglycol isomer.
Above-mentioned various butyleneglycol isomer are 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol and 2,3-butyleneglycol.
Above-mentioned C
6The weight that row hydrocracking generates polyol blends during sugar alcohol consists of: ethylene glycol 20-50%, and propylene glycol 35-65%, glycerol 10-20%, various butyleneglycol isomer 8-20% remain and are the less fusel of other content.
Above-mentioned C
6Sugar alcohol is to be preferably corn with cereal, is made into starch, generates glucose, repeated hydrogenation and make through liquefying-saccharifying.
The present invention is with respect to prior art, and its advantage is as follows:
The present invention is with C
6Sugar alcohol is a raw material, through obtaining relevant dibasic alcohol and polyvalent alcohol such as ethylene glycol, propylene glycol, glycerol, butyleneglycol after high temperature, the high pressure cracking.Production method advantage of the present invention is to produce the route novelty, the processing condition uniqueness, and easy to operate, technology is simple, and can produce multiple dibasic alcohol and polyvalent alcohol, good product quality simultaneously.And can cereal such as corn be raw material production C
6Sugar alcohol promptly can replace Nonrenewable resources by renewable resources, and the quality product performance is better than the alcohols of additive method production, and there is very big advantage its production and raw material aspect.
Embodiment
The starting material that production method adopted of chemical industry alcohol of the present invention are C
6Sugar alcohol, it can be the C that buys on the market
6Sugar alcohol also can be to be raw material with cereal, adopts ordinary method to produce starch, generates glucose through liquefying-saccharifying, produces C used in the present invention by hydrogenation again
6Sugar alcohol.
Basic raw material of the present invention is a starch, for example corn can be changed into starch milk after, direct liquefaction, saccharification are produced glucose.Generate glucose solution, liquid C is produced in the high-pressure hydrogenation reaction under the nickel catalyzator effect
6Sugar alcohol, under the catalyst for cracking effect, C
6The further hydrocracking of sugar alcohol generates described chemical industry alcohol.
List reaction formula explanation below:
1, the production of glucose
2, the production of C6 sugar alcohol
3, with C
6Sugar alcohol obtains correspondent alcohol for the raw material hydrogenation.
1) ethylene glycol:
2) propylene glycol:
3) glycerol:
4) butyleneglycol:
The isomers of butyleneglycol has four kinds:
1,2-butyleneglycol 1,3 butylene glycol 1,4-butyleneglycol 2,3-butyleneglycol
The present invention can be raw material production C by cereal such as corn
6Sugar alcohol, its production method is as follows:
According to a conventional method, corn is changed into starch milk, in the presence of amylase and saccharifying enzyme, Liquid Glucose with water generation 70-76%, in about 24 ℃ of following crystallisation by cooling, obtain about 60% damp sugar soln after the centrifugation, then, in the presence of common nickel catalyzator, carry out hydrogenation reaction in 150-160 ℃ and pressure 10MPa and hydrogen and make C
6Sugar alcohol.
Chemical industry alcohol production method of the present invention comprises the steps:
One, the production of chemical industry alcohol mixture:
1) C
6The sugar alcohol solution feed proportioning:
With C
6Sugar alcohol mixes by a certain percentage with water and alkali; In order better to control reaction result and reaction yield, the compound concentration of C6 sugar alcohol solution is about 30-60% (Wt/V), C during mixing
6Sugar alcohol and mol ratio hydroxy are 3-14:1, and the best is 4; C
6The sugar alcohol solution pH value is 11-13.5, and the best is 13;
2) preheating of raw material:
For the hydrocracking reaction can be produced a desired effect, raw material should carry out preheating earlier before entering reactor, the stock liquid after the preparation is heated to about 180-220 ℃, uses with the hydrogenation reaction of supplying with next step;
3) preheating of new hydrogen:
For the hydrocracking reaction can be produced a desired effect, new hydrogen should carry out preheating earlier before entering reactor, new hydrogen is heated to about 230-250 ℃, uses with the hydrogenation reaction of supplying with next step;
4) hydrogenation reaction:
Hydrogenation reaction is to require the strictest part in the entire operation process, and the temperature of reaction of hydrogenation reaction is 230-250 ℃, and reaction pressure is 10-15MPa, and the reaction times is about 40-60 minute.Under such reaction conditions, C
6Sugar alcohol generation chemical reaction generates the chemical industry alcohol of wanting required for the present invention.
Two, the separation of chemical industry alcohol mixture:
1) dehydration:
Water in the chemical industry alcohol mixture is all removed by the continuous glue of dehydration rectifying tower, can in the separation and purification process, obtain purified component like this;
2) take off heavily:
With some heavier component: C in the chemical industry alcohol mixture
6Sugar alcohol, glycerol, organic acid salt are removed continuously by taking off heavy rectifying tower, so that obtain the purified component of dibasic alcohol required for the present invention;
3) refining:
With the chemical industry alcohol (being mainly dibasic alcohol) after the heavy constituent of dewatering, take off, by a plurality of product rectifying tower such as packing tower, according to each component volatilization degree and different, can one by one it be separated, obtain pure component ethylene glycol, propylene glycol and the various butyleneglycol isomer of wanting etc. required for the present invention respectively.
If comprise by starch milk and produce C
6Sugar alcohol and by the operation of methanol decomposition hydrogen manufacturing, apparatus of the present invention are divided into four parts: promptly raw material receive, accumulating finished product packing workshop section; The gassing recycle section is adsorbed, separated to methanol decomposition, transformation; Reaction workshop section; Dehydration, four parts of separation and product purification workshop section.Raw material receives the main molasses that receive the glucose syrup of starch milk conversion or directly buy and produces C
6Sugar alcohol, to also have raw materials such as some subsidiary material alkali, methyl alcohol, hydrogen manufacturing workshop section in addition be to utilize methyl alcohol to make qualified hydrogen for reaction usefulness, and reaction workshop section is the core workshop section of this device, C
6Sugar alcohol generates the product of various needs.As propylene glycol, ethylene glycol, glycerol, the isomers of various butyleneglycols, and byproduct such as methyl alcohol, ethanol.
1.C
6The production of sugar alcohol:
1000 kilograms of corns are changed into starch milk (700 kilograms of butts), in the presence of amylase and saccharifying enzyme, with aquatic Liquid Glucose into about 742 kilogram 70%, in 24 ℃ of following crystallisation by cooling, obtain 865 kilogram 60% damp sugar soln after the centrifugation, then, in the presence of nickel catalyzator, carry out 860 kilograms of C of hydrogenation reaction shooting with about 10MPa and hydrogen in 156 ℃
6Sugar alcohol is with to be used.
2. the production of hydrogen:
325 kilograms of/hour methyl alcohol and 183 kilograms of/hour de-salted waters are mixed, and being superheated to temperature of reaction through pressurization, preheating, vaporization is 260 ℃, in the about 0.9MPa of reaction pressure, in the presence of catalyzer, carry out conversion reaction, obtain about 900Nm3/ hour reforming gas, wherein hydrogen content is 73-74.5%.Again pyrolytic conversion gas is cooled off, is condensed to below 40 ℃, after conventional method is refining, get 〉=99.5% hydrogen, with to be used.
3. chemical industry alcohol (is mainly C
2-4Dibasic alcohol) production:
Produce the chemical industry alcohol mixture of 1000Kg/h, promptly drop into 70%C6 sugar alcohol 450Kg/h, and add water 550Kg/h and be diluted to concentration 45% (Wt/V), adjust solution pH value to 13, C with alkali then
6Sugar alcohol is after 4:1 mixes with the hydroxide radical mol ratio, with stock liquid through being preheated to 180-220 ℃, then, enter reactor, under nickel/palladium catalyst for cracking effect be preheated to hydrogen the hydrocracking reaction take place under high temperature 230-250 ℃, high pressure 12MPa, obtain the 1000Kg/h reaction product, mainly contain ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,4-butyleneglycol, 2, the mix products of 3-butyleneglycol, glycerol, methyl alcohol, ethanol, methane etc.In addition, also has the unconverted C of part
6The heavy constituent that produce in sugar alcohol and the reaction process, after separating, turn back to hydrogenation reaction workshop section, again prepare burden, and then enter reactor, carry out hydrocracking, thereby make raw material fully obtain utilize reducing reaction cost, product basin in the middle of cracking products therefrom and hydrogenation products therefrom for the first time are mixed and enter, separation circuit to be entered.Hydrogenation products composed as follows:
| Title | Form Wt% |
| Methyl alcohol | 0.44 |
| Ethanol | 0.18 |
| C 6Sugar alcohol | 2.06 |
| Formate | 3.6 |
| Acetate | 0.71 |
| Lactic acid salt | 3.65 |
| Propylene glycol | 15.67 |
| Ethylene glycol | 8.45 |
| Glycerol | 4 |
| 1, the 2-butyleneglycol | 1.15 |
| 2, the 3-butyleneglycol | 1.79 |
| 1,3 butylene glycol | 0.08 |
| 1, the 4-butyleneglycol | 0.18 |
| NaOH | 0.71 |
| H2O | 52.73 |
| Other | 4.6 |
| Add up to Kg/h | 1000 |
With the chemical industry alcohol mixture of the above-mentioned composition of 1000Kg/h gained, through dehydration, take off the heavy constituent operation with moisture in the product and C
6Sugar alcohol, glycerol and heavy constituent (organic salt) etc. remove, and carry out C by a plurality of product rectifying tower then
2-4Di-alcohols refining obtains byproducts such as the single product of various alcohols and first, ethanol after the separation.
Claims (8)
1, a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, it is characterized in that: this method is included in alkaline condition and nickel/palladium catalyst for cracking exists down, at aqueous phase C
6The proportioning of sugar alcohol in the aqueous solution is 30-60%, and unit is: Wt/V; C
6The mol ratio of sugar alcohol and hydroxide ion is 3-14:1, with C
6The sugar alcohol hydrogenation cracking generates the mixture of polyvalent alcohol, obtains single or mixing prod behind separation and purification respectively.
2, according to claim 1 a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, it is characterized in that: at aqueous phase C
6The proportioning of sugar alcohol in the aqueous solution is 45%, and unit is: Wt/V; C
6The mol ratio of sugar alcohol and sodium hydroxide is 4:1.
3, according to claim 1 and 2 a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, and it is characterized in that: described hydrocracking is 225-260 ℃ in temperature of reaction, and optimal temperature is 240 ℃, and reaction pressure is 10-15MPa, and optimum pressure is 12MPa.
4, according to claim 3 a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, it is characterized in that: the C of described preparation
6The sugar alcohol solution pH value is 12-13.5, and the optimum pH value is 13; Reaction times is 40-60 minute, and the optimum time is 60 minutes.
5, according to claim 3 a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, and it is characterized in that: described chemical industry alcohol is C
2-4Dibasic alcohol, dibasic alcohol are ethylene glycol, propylene glycol and various butyleneglycol isomer.
6, according to claim 5 a kind of by C
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, and it is characterized in that: described various butyleneglycol isomer are 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol and 2,3-butyleneglycol.
7, each is described a kind of by C according to claim 5
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, it is characterized in that: described C
6Sugar alcohol carries out the weight that hydrocracking generates polyol blends and consists of: ethylene glycol 20-50%, and propylene glycol 35-65%, glycerol 10-20%, various butyleneglycol isomer 8-20% remain and are the less fusel of other content.
8, each is described a kind of by C according to claim 3
6The method of chemical industry alcohol is produced in the cracking of sugar alcohol water, it is characterized in that: described C
6Sugar alcohol is to be preferably corn with cereal, is made into starch, generates glucose, repeated hydrogenation and make through liquefying-saccharifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810017788A CN101544537A (en) | 2008-03-25 | 2008-03-25 | Method for producing low carbon chemical ethanol from C6 sugar alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810017788A CN101544537A (en) | 2008-03-25 | 2008-03-25 | Method for producing low carbon chemical ethanol from C6 sugar alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101544537A true CN101544537A (en) | 2009-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810017788A Pending CN101544537A (en) | 2008-03-25 | 2008-03-25 | Method for producing low carbon chemical ethanol from C6 sugar alcohol |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311312A (en) * | 2010-07-09 | 2012-01-11 | 郸城财鑫糖业有限责任公司 | Method for producing 1,6-hexanediol by cracking sorbierite |
| CN102391065A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for producing dihydric alcohol and low molecular polyalcohol by taking corn husk as raw material |
| 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 |
| CN103664459A (en) * | 2013-11-12 | 2014-03-26 | 嘉兴香料厂 | Production process for continuously fractionating and purifying dihydromyrcene by using two towers |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| EP3653595A1 (en) | 2014-09-28 | 2020-05-20 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for preparing diol |
-
2008
- 2008-03-25 CN CN200810017788A patent/CN101544537A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311312A (en) * | 2010-07-09 | 2012-01-11 | 郸城财鑫糖业有限责任公司 | Method for producing 1,6-hexanediol by cracking sorbierite |
| CN102391065A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for producing dihydric alcohol and low molecular polyalcohol by taking corn husk as raw material |
| 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 |
| CN102391065B (en) * | 2011-08-09 | 2014-02-05 | 山东省鲁洲食品集团有限公司 | Method for producing dihydric alcohol and low molecular polyalcohol by taking corn husk as raw material |
| CN103664459A (en) * | 2013-11-12 | 2014-03-26 | 嘉兴香料厂 | Production process for continuously fractionating and purifying dihydromyrcene by using two towers |
| EP3653595A1 (en) | 2014-09-28 | 2020-05-20 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for preparing diol |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
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Open date: 20090930 |