CN102030612A - Method for preparing n-butyl alcohol by utilizing alcohol-containing waste liquid - Google Patents
Method for preparing n-butyl alcohol by utilizing alcohol-containing waste liquid Download PDFInfo
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- CN102030612A CN102030612A CN201010568079XA CN201010568079A CN102030612A CN 102030612 A CN102030612 A CN 102030612A CN 201010568079X A CN201010568079X A CN 201010568079XA CN 201010568079 A CN201010568079 A CN 201010568079A CN 102030612 A CN102030612 A CN 102030612A
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- propyl carbinol
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Abstract
The invention relates to a method for preparing n-butyl alcohol by utilizing an alcohol-containing waste liquid. On the basis of the principle that a hydrogenation reaction can be carried out on unsaturated organic compounds in presence of catalysts to generate saturated hydrocarbon or derivatives thereof, and selective hydrogenation is carried out on toxic low-carbon linear chain unsaturated alcohol and/or unsaturated aldehyde in the alcohol-containing waste liquid by the catalysts, so as to generate desired product-n-butyl alcohol. In the whole method, the procedure is simple, the condition is easy to control, the product yield is high, the butyl alcohol products have high purity, the equipment investment is low, the production cost is low, the energy consumption is saved, the method is hopeful to be applied to the recovery processing of the alcohol-containing waste liquid in the production process such as butanediol production process and the like, the production additional value is improved, and the environment pollution is reduced, therefore, the method has very important economic significance and social significance.
Description
Technical field
The present invention relates to a kind of utilization and contain the method that pure waste liquid prepares propyl carbinol.
Background technology
The method of synthesizing butanol mainly is to be raw material with the Sweet natural gas on the traditional industry, and metallic nickel is a catalyzer.Directly transform by Sweet natural gas and water vapour, during conversion with CO, CO
2, side reaction such as charing, must increase postprocessing working procedures, aftertreatment need denitrogenate also that to handle repeated hydrogenation saturated through conversion and decarburization, cryogenic purification, carries out the rectification and purification of propyl carbinol at last.Production process is numerous and diverse, the operational condition harshness, and the energy consumption height, product yield is low, and the three wastes are handled difficult, cost of equipment height, cost height.
Producing 1, can produce the organic useless pure liquid of a large amount of higher concentrations in 4-butyleneglycol (BDO) process, wherein containing the BuOH(butanols), water and the like methyl alcohol of other alcohols, propyl alcohol, propargyl alcohol, butynediol etc.Easily form two-phase and the low azeotropic mixture that boils in the waste liquid that BDO produces under given component condition, at distillation tower, each component of azeotrope is difficult to separate.In recent years, because 1, the greatly developing of 4-butyleneglycol etc., the processing of the organic useless pure liquid of its tankage also becomes an extremely urgent difficult problem.Produce 1, in the organic useless pure liquid that the 4-butyleneglycol is produced, the alcohols industrial chemicals content of recyclable utilization is up to more than 50%, its existing treatment process takes incinerating method to handle mostly, so not only wasted wherein callable organic products, more atmosphere is polluted, also cause the wasting of resources, one ton of useless pure liquid of every processing needs the processing costs of 200-500 unit approximately.At present, to the also advanced without comparison technology of the processing of this type of organic useless pure liquid water, a lot of organic constituents are difficult to decompose in the world.Domestic and even the world does not all also have to contain the technology that poisonous component decomposes in the pure waste liquid.
Provide a kind of utilization to contain the method that pure waste liquid prepares propyl carbinol, be used for the recycling that production technique such as butyleneglycol contains pure waste liquid, improve the production added value, reduce environmental pollution, become problem demanding prompt solution.
Summary of the invention
Of the present inventionly be to provide a kind of utilization to contain the method that pure waste liquid prepares propyl carbinol, be used for the recycling that production technique such as butyleneglycol contains pure waste liquid, improve the production added value, reduce environmental pollution; Simultaneously, operation is simple, and condition is easily controlled, the product yield height, and the butanols good product purity, facility investment is few, and production cost is low, energy efficient.
Purpose of the present invention is achieved through the following technical solutions:
Utilization contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: comprise the steps:
A. get and contain pure waste liquid and add catalyzer, under hydrogenation conditions, feed hydrogen, reaction solution;
B. reaction solution is carried out rectification and purification, purity is not less than 99% propyl carbinol.
Contain carbonatoms be not more than 4 straight chain unsaturated alcohol and/or unsaturated aldehyde described containing in the pure waste liquid, and when the unsaturated alcohol carbonatoms is not more than 3, feed the aldehyde that can generate C4 straight chain unsaturated alcohol with unsaturated alcohol generation catalyzed reaction in containing pure waste liquid;
Described catalyzer comprises the catalysis major constituent that is made of carrier and catalytic active component, and carrier is an activated alumina, catalytic active component Cu
+(CCCC-) Cu
+And Ni
+(CCCC-) Ni
+
Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 40-50%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 19-25%.
Preferably, contain propargyl alcohol, 1 described containing in the pure waste liquid, 4-butynediol, 1, and at least a in 4-butylene glycol, 4-hydroxyl-butanone, fourth-3-olefine aldehydr and the but-2-ene aldehyde, and when containing propargyl alcohol, in containing pure waste liquid, feed formaldehyde;
Preferably, Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 45%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 20%, and the carrier size range is 1.5-2mm;
Preferably, described hydrogenation conditions is: 88 ℃～98 ℃ of hydrogenation temperatures, reaction pressure are 1.5-2Bar;
Preferably, described rectifying comprises following operation steps:
(1) by selective solvent reaction solution is extracted in advance, get the rich layer of propyl carbinol;
(2) described rich layer introducing rectifying tower is carried out rectification and purification, obtain the propyl carbinol of required purity.
Preferably, described extractive distillation column is solid valve tower tray rectifying tower;
Preferably, the water of the middle gained of step (2) is as heat-eliminating medium recycle in cooling system.
The present invention is based on unsaturated organic compound and in the presence of catalyzer, can carry out the principle that hydrogenation reaction generates saturated hydrocarbon or derivatives thereof, make by catalyzer to contain deleterious low-carbon (LC) straight chain unsaturated alcohol and/or unsaturated aldehyde generation selective hydrogenation in the pure waste liquid, generate purpose product propyl carbinol; Selected catalyzer has better hydrogenation activity to unsaturated alcohol and unsaturated aldehyde, can contain unsaturated alcohols in the pure waste liquid in catalysis under the demulcent condition comparatively, impurity in the effective elimination solution, reduce solution toxicity, improve the quality of products, and have the life-span long, intensity is high, high temperature resistant, consumption is few, not etching apparatus, environment amenable advantage.
The entire method operation is simple, condition is easily controlled, the product yield height, the butanols good product purity, facility investment is few, production cost is low, energy efficient is expected to be applied to the recycling that contains pure waste liquid in the production technique such as butyleneglycol, is improving the production added value, reduce the environmental pollution aspect, have important economic implications and social effect.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is further described.
Accompanying drawing is a propyl carbinol preparation technology schema.
Embodiment
The preparation catalyzer:
A. by the theoretical content of copper and mickel in the catalysis major constituent, the powder of getting copper carbonate and nickelous carbonate adds in the Preparation of Catalyst reactor;
B. in reactor, add the formaldehyde solution of 50%-55% mass concentration, 35-45 times copper carbonate and nickelous carbonate gross weight, stir, get mixture;
C. heat and feed acetylene behind the described mixture to 75 ℃ and insulation reaction generates to no longer including carbonic acid gas;
D. after in material in reactor, adding the alumina catalyst support of described granularity by the theoretical content of carrier in the catalysis major constituent and stirring, the catalyzer of paste-like.
The Preparation of Catalyst principle is as follows:
2Cu
2+?+?2e
-?→?2Cu
+
HCHO?+?2OH
-?→?HCOOH?+?H
2O?+?2e
-
Cu
+?+?Ni
2++3e
-+?CO
3 2-?→?Cu+?Ni+?CO
3 2-
Cu
+?+?H
++2e
-?+?CO
3 2-?→Cu?+?H+?CO
3 2-
After feeding acetylene:
2HCCH?+?2OH
-?→?HCCCCH?+?2H
2O?+?2e
-
2HCCCCH+?+2CO
3 2-+2Cu+2Ni→Cu
+(CCCC-)Cu
++?Ni
?+(CCCC-)?Ni
?+?+2H
2O?+2CO
2
Embodiment one:
Get Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 40%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 19%, and the carrier granularity is 1.5mm; Getting the formaldehyde mass concentration is 50%, and formaldehyde weight is copper carbonate and nickelous carbonate gross weight 35 times; Among the step c, it is 30Kpa that control acetylene feeds pressure; Get catalyst A.
Embodiment two:
Get Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 50%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 25%, and the carrier granularity is 2mm; Getting the formaldehyde mass concentration is 52%, and formaldehyde weight is copper carbonate and nickelous carbonate gross weight 45 times; Among the step c, it is 38Kpa that control acetylene feeds pressure; Get catalyst B.
Embodiment three:
Get Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 45%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 20%, and the carrier granularity is 2mm; Getting concentration of formaldehyde is 55%, and formaldehyde weight is copper carbonate and nickelous carbonate gross weight 40 times; Among the step c, it is 45Kpa that control acetylene feeds pressure; Get catalyzer C.
The physicochemical characteristics of each embodiment gained catalyst prod is as follows:
Table 1
The preparation of propyl carbinol:
Get BDO(1, the 4-butyleneglycol) by-product in the production technique contains pure waste liquid, and employing table 1 gained catalyzer carries out catalytic hydrogenation reaction and prepares propyl carbinol, contains the composition such as the table 2 of pure waste liquid:
Table 2
The catalytic hydrogenation reaction principle is as follows:
H
2C=O+HC ≡ CH-catalyzer → HC ≡ C-CH
2-OH
HC ≡ C-CH
2-OH+ H
2C=O-catalyzer → HO-H
2C-C ≡ C-CH
2-OH
HO-H
2C-C ≡ C-CH
2-OH+H
2-catalyzer → HO-CH
2-CH=CH-CH
2-OH+Q
HO-CH
2-CH=CH-CH
2-OH+H
2-catalyzer → HO-CH
2-CH
2-CH
2-CH
2-OH+Q
The preparation of propyl carbinol is undertaken by following operation: adding is preheated to pure waste liquid 80 ℃ contain continuously in the hydrogenation still, add the catalyzer in the table 1, under hydrogenation conditions in containing pure waste liquid: the weight ratio of hydrogen is (1-2): (1.75-3) ratio feeds hydrogen and carries out hydrogenation, reaction solution; The gained reaction solution is imported screen decanter, and the screen decanter upper strata obtains the rich layer of propyl carbinol, and the bottom obtains containing 80% water and Shuifu County's layer of other alcohols; The rich layer of propyl carbinol feeds the rectifying tower with 25 solid valve tower trays, particularly be to enter from No. 15 tower trays, rectifying tower moves under atmospheric pressure conditions, the vapour mixture of rectifying tower cat head output is by the overhead condenser condensing reflux, reflux ratio is 2-3.5, at the bottom of the rectifying Tata, obtain the propyl carbinol product, the rectifying tower overhead product can further prepare butyleneglycol and tetrahydrofuran (THF) etc. by rectification and purification according to prior art, in the present embodiment, the selection standard of selective solvent is: it is higher to get boiling point, and the solvent with arbitrary component formation azeotrope does not get final product, thereby its purpose is the relative volatility that only changes original component and realizes rectifying separation, in the present embodiment, selective solvent is the rectifying tower overhead product, can destroy the azeotropic point of propyl carbinol and other alcohols, the extraction yield height of propyl carbinol, extraction effect is good, and is practical more economically.
In present method, gained Shuifu County layer can be sent to the ethanol vapor stripper by the alcohols in the rich layer of low-pressure steam gas water lift, gas stripping column moves under barometric point equally, gas stripping column top gained vapour mixture is by after the potato spirit condenser condenses, mix the formation potato spirit with the rectifying tower overhead product, the water of stripping tower bottom cleaning after testing, COD directly enters sewerage less than 100PPm.
Embodiment 1
In the present embodiment, getting hydrogen is 1.75:1 with the weight ratio that contains pure waste liquid, and hydrogenation conditions is: 80-83 ℃ of hydrogenation temperature (being reaction solution liquid temperature), and reaction pressure 1.5Bar, all the other conditions and catalytic hydrogenation reaction the results are shown in Table 3.
Table 3
| Catalyzer | The catalyzed reaction time | The propyl carbinol yield | Propyl carbinol purity |
| A | 0.48h | 92% | 99.2% |
| B | 0.7h | 93% | 99.5% |
| C | 1.1h | 92% | 99.3% |
Example 2:In the present embodiment, getting hydrogen is 2:1.75 with the weight ratio that contains pure waste liquid, and hydrogenation conditions is: 100 ℃～105 ℃ of hydrogenation temperatures, and reaction pressure 2Bar, all the other conditions and catalytic hydrogenation reaction the results are shown in Table 4.
Table 4
| Catalyzer | The catalyzed reaction time | The propyl carbinol yield | Propyl carbinol purity |
| A | 1.5h | 91% | 99.4% |
| B | 0.9h | 92% | 99.1% |
| C | 0.5h | 93% | 99.3% |
Example 3:In the present embodiment, getting hydrogen is 3:2 with the weight ratio that contains pure waste liquid, and hydrogenation conditions is: 128 ℃～130 ℃ of hydrogenation temperatures, and reaction pressure 1.75Bar, all the other conditions and catalytic hydrogenation reaction the results are shown in Table 5.
Table 5
| Catalyzer | The catalyzed reaction time | The propyl carbinol yield | Propyl carbinol purity |
| A | 1.2h | 93% | 99.2% |
| B | 2h | 91% | 99.3% |
| C | 0.7h | 92% | 99.2% |
Claims (7)
1. utilize to contain the method that pure waste liquid prepares propyl carbinol, it is characterized in that: comprise the steps:
A. get and contain pure waste liquid and add catalyzer, under hydrogenation conditions, feed hydrogen, reaction solution;
B. reaction solution is carried out rectification and purification, purity is not less than 99% propyl carbinol.
Contain carbonatoms be not more than 4 straight chain unsaturated alcohol and/or unsaturated aldehyde described containing in the pure waste liquid, and when the unsaturated alcohol carbonatoms is not more than 3, feed the aldehyde that can generate C4 straight chain unsaturated alcohol with unsaturated alcohol generation catalyzed reaction in containing pure waste liquid;
Described catalyzer comprises the catalysis major constituent that is made of carrier and catalytic active component, and carrier is an activated alumina, and catalytic active component comprises Cu
+(CCCC-) Cu
+And Ni
+(CCCC-) Ni
+
Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 40-50%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 19-25%.
2. utilization according to claim 1 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: contain propargyl alcohol, 1 described containing in the pure waste liquid, 4-butynediol, 1, at least a in 4-butylene glycol, 4-hydroxyl-butanone, fourth-3-olefine aldehydr and the but-2-ene aldehyde, and when containing propargyl alcohol, in containing pure waste liquid, feed formaldehyde.
3. utilization according to claim 1 and 2 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: Cu
+(CCCC-) Cu
+Massfraction in the catalysis major constituent is 45%, Ni
+(CCCC-) Ni
+Massfraction in the catalysis major constituent is 20%, and the carrier size range is 1.5-2mm.
4. utilization according to claim 3 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: described hydrogenation conditions is: 88 ℃～98 ℃ of hydrogenation temperatures, reaction pressure are 1.5-2Bar.
5. utilization according to claim 4 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that:
Described rectifying comprises following operation steps:
(1) by selective solvent reaction solution is extracted in advance, get the rich layer of propyl carbinol;
(2) described rich layer introducing rectifying tower is carried out rectification and purification, obtain the propyl carbinol of required purity.
6. utilization according to claim 5 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: described extractive distillation column is solid valve tower tray rectifying tower.
7. utilization according to claim 6 contains the method that pure waste liquid prepares propyl carbinol, it is characterized in that: the water of step (2) gained is as heat-eliminating medium recycle in cooling system.
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|---|---|---|---|
| CN 201010568079 CN102030612B (en) | 2010-12-01 | 2010-12-01 | Method for preparing n-butyl alcohol by utilizing alcohol-containing waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010568079 CN102030612B (en) | 2010-12-01 | 2010-12-01 | Method for preparing n-butyl alcohol by utilizing alcohol-containing waste liquid |
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| CN102030612B CN102030612B (en) | 2013-03-06 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262097A (en) * | 2014-09-12 | 2015-01-07 | 迪邦（泸州）化工有限公司 | Method for innocent treatment of BDO organic wastewater |
| CN105439820A (en) * | 2015-11-19 | 2016-03-30 | 迪邦（泸州）化工有限公司 | Method for innocently treating organic waste liquid generated in BDO production |
| CN106336061A (en) * | 2016-10-31 | 2017-01-18 | 万华化学集团股份有限公司 | Method for treating high-concentration isobutylene wastewater through PO by-product TBA pyrolysis |
| CN106349018A (en) * | 2016-07-29 | 2017-01-25 | 迪邦（泸州）化工有限公司 | Method for harmlessly treating BDO organic waste liquid |
| CN107129424A (en) * | 2017-06-27 | 2017-09-05 | 查都（上海）科技有限公司 | A kind of butanediol and n-butanol purification system |
| CN113929558A (en) * | 2021-10-13 | 2022-01-14 | 中国海洋石油集团有限公司 | Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production |
| CN114315523A (en) * | 2022-01-13 | 2022-04-12 | 万华化学集团股份有限公司 | Method for recovering waste liquid from preparation of 1, 4-butanediol by epoxypropane method |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262097A (en) * | 2014-09-12 | 2015-01-07 | 迪邦（泸州）化工有限公司 | Method for innocent treatment of BDO organic wastewater |
| CN104262097B (en) * | 2014-09-12 | 2016-04-06 | 迪邦（泸州）化工有限公司 | A kind of method of harmless treatment BDO organic liquid waste |
| CN105439820A (en) * | 2015-11-19 | 2016-03-30 | 迪邦（泸州）化工有限公司 | Method for innocently treating organic waste liquid generated in BDO production |
| CN106349018A (en) * | 2016-07-29 | 2017-01-25 | 迪邦（泸州）化工有限公司 | Method for harmlessly treating BDO organic waste liquid |
| CN106349018B (en) * | 2016-07-29 | 2019-04-12 | 迪邦（泸州）化工有限公司 | A kind of method of harmless treatment BDO organic liquid waste |
| CN106336061A (en) * | 2016-10-31 | 2017-01-18 | 万华化学集团股份有限公司 | Method for treating high-concentration isobutylene wastewater through PO by-product TBA pyrolysis |
| CN106336061B (en) * | 2016-10-31 | 2020-01-31 | 万华化学集团股份有限公司 | Treatment method of high-concentration wastewater from cracking PO byproduct TBA to prepare isobutene |
| CN107129424A (en) * | 2017-06-27 | 2017-09-05 | 查都（上海）科技有限公司 | A kind of butanediol and n-butanol purification system |
| CN113929558A (en) * | 2021-10-13 | 2022-01-14 | 中国海洋石油集团有限公司 | Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production |
| CN113929558B (en) * | 2021-10-13 | 2023-12-22 | 中国海洋石油集团有限公司 | Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production |
| CN114315523A (en) * | 2022-01-13 | 2022-04-12 | 万华化学集团股份有限公司 | Method for recovering waste liquid from preparation of 1, 4-butanediol by epoxypropane method |
| CN114315523B (en) * | 2022-01-13 | 2023-12-19 | 万华化学集团股份有限公司 | Waste liquid recovery method for preparing 1, 4-butanediol by epoxypropane method |
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