CN1261399C - Preparation method for isopentyl aldehyde - Google Patents
Preparation method for isopentyl aldehyde Download PDFInfo
- Publication number
- CN1261399C CN1261399C CNB031292003A CN03129200A CN1261399C CN 1261399 C CN1261399 C CN 1261399C CN B031292003 A CNB031292003 A CN B031292003A CN 03129200 A CN03129200 A CN 03129200A CN 1261399 C CN1261399 C CN 1261399C
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- CN
- China
- Prior art keywords
- reaction
- copper
- preparation
- isoamyl alcohol
- present
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 isopentyl aldehyde Chemical class 0.000 title abstract 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 9
- 239000010951 brass Substances 0.000 claims abstract description 9
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 4
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 4
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 44
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002309 gasification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing isopentyl aldehyde by using isoamyl alcohol as initial raw material. A method for preparing isopentyl aldehyde by using an Ag/KZSM-5 molecular sieve as a catalyst exists with very large potential safety hazard, the catalyst has the disadvantages of hard preparation, high cost, short service life and high productive energy consumption, and the quantity of oxygen in the process of reaction is hard to control. The present invention is characterized in that isoamyl alcohol is heated until phenomenon of gasification occurs, and then reaction of high-temperature catalytic dehydrogenation is carried out by using brass catalysts; gas generated in the reaction is condensed and separated to obtain products of isopentyl aldehyde, and the brass catalysts are copper/zinc alloys, copper/tin alloys or copper/nickel alloys. The present invention can not generate corrosion to equipment besides ensuring high conversion rate and selectivity, and environmental pollution is less; additionally, the present invention has the advantages of easy preparation of catalysts, low cost, long service life and high production safety.
Description
Technical field
The present invention relates to a kind of is the method that starting raw material prepares isovaleric aldehyde with the primary isoamyl alcohol.
Background technology
Isovaleric aldehyde is raw material, the intermediate of compound essence spices and the raw material of foodstuffs industry and pharmaceutical industry of making isovaleric acid.The preparation method of isovaleric aldehyde mainly adopts oxidation style at present, with sulfuric acid, dichromic acid (salt), Cr
2O
3, MnO
2Deng primary isoamyl alcohol being oxidized to isovaleric aldehyde in liquid phase, sulfuric acid, dichromic acid (salt) are serious to equipment corrosion, and environmental pollution is big, and the side reaction of generation is many; Use Cr
2O
3, MnO
2Though high etc. selectivity, the catalyzer cost is higher.
Delivered one piece " research that the last primary isoamyl alcohol catalyzed oxidation of Ag/KZSM-5 is an isovaleric aldehyde " on the 27th volume the 4th phase (1998) " Guangxi chemical industry ", it discloses a kind of method for preparing isovaleric aldehyde with primary isoamyl alcohol, this method is a catalyzer with the Ag/KZSM-5 molecular sieve, under the heating hot conditions, bubbling air carries out catalyzed oxidation, this technology environmental pollution is few, transformation efficiency and selectivity height, but Preparation of Catalyst is difficult for, use precious metals ag, Preparation of Catalyst cost height, work-ing life is short, the production energy consumption height; And the oxygen amount in the reaction is wayward, and the excessive meeting of oxygen makes isovaleric aldehyde or primary isoamyl alcohol that deep oxidation at high temperature take place, even generates CO
2And H
2O.In addition, under the high temperature aerobic conditions, there is very big potential safety hazard in the limits of explosion wide ranges of primary isoamyl alcohol and isovaleric aldehyde; Simultaneously, contain a large amount of organic gas in the tail gas with excess air (oxygen) discharge, very easily blast.Under the situation that does not solve above-mentioned safety problem, aforesaid method is difficult to realize suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes prior art, a kind of preparation method who primary isoamyl alcohol is carried out the isovaleric aldehyde of high-temperature catalytic dehydrogenation with brass class catalyzer is provided, guaranteeing under high conversion and the selectivity, equipment there is not corrosion, pollute few, the production security height, the easy and long service life of Preparation of Catalyst.
Technical scheme of the present invention is such: the preparation method of isovaleric aldehyde, it is characterized in that heating primary isoamyl alcohol to vaporization, carry out the high-temperature catalytic dehydrogenation reaction with brass class catalyzer then, the gas that reaction produces obtains the product isovaleric aldehyde after condensation, separation, described brass class catalyzer is copper/zinc alloy, copper/tin alloy or copper/nickelalloy.The present invention is gas phase continuous catalysis dehydrogenation reaction, and is safe; Catalyzer of the present invention is an alloy type, and preparation is easy, and cost is low, and long service life can not produce corrosion to equipment, and is low in the pollution of the environment.The isovaleric aldehyde that the present invention obtains has high conversion and selectivity equally.
The preparation method of described isovaleric aldehyde, brass class catalyzer is netted, in the fixed-bed reactor of packing into the vaporization after primary isoamyl alcohol carry out the high-temperature catalytic dehydrogenation reaction, the specific surface area of netted catalyst is big, makes the better effects if of catalytic dehydrogenation.
The preparation method of described isovaleric aldehyde, the air speed of catalyzer is 0.3～0.5/h (air speed: the liquid bulk product that passes through the given volume catalyzer in the unit time), the input speed of primary isoamyl alcohol is 200～380ml/h, vaporization temperature is at 160～240 ℃, the temperature of reaction of catalytic dehydrogenation is at 400～500 ℃, the selectivity of the present invention's gained in above-mentioned processing range is more than 99%, and molar yield (transformation efficiency) is more than 95%.
Technology of the present invention is simple, is guaranteeing that have the following advantages: 1) catalyzer is an alloy type, is netted under high conversion and the selectivity, and specific surface area is big, and catalytic dehydrogenation is effective, long service life; 2) can not produce corrosion to equipment, low in the pollution of the environment; 3) Preparation of Catalyst is easy, and cost is low; 4) be gas phase continuous catalysis dehydrogenation reaction, the production security height is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
100 gram raw material primary isoamyl alcohol (content 99%) are delivered to preheater continuously by pump and are vaporized, the control input speed is about 300ml/h, the temperature of preheater is controlled at 200 ℃, enters air speed then and is in the fixed-bed reactor of netted copper/zinc alloy of 0.45/h, is heated to 460 ℃, reaction product enters the condenser cooling, after decompression distillation separates, obtain product isovaleric aldehyde 94.3 grams, through gas chromatographic analysis, content 〉=99.0% (m/m), transformation efficiency are 96.5%.
Embodiment 2
100 gram raw material primary isoamyl alcohol (content 99%) are delivered to preheater continuously by pump and are vaporized, the control input speed is about 260ml/h, the temperature of preheater is controlled at 240 ℃, enters air speed then and is in the fixed-bed reactor of netted copper/tin alloy of 0.5/h, is heated to 480 ℃, reaction product enters the condenser cooling, after decompression distillation separates, obtain product isovaleric aldehyde 92.8 grams, through gas chromatographic analysis, content 〉=99.0% (m/m), transformation efficiency are 95%.
Embodiment 3
100 gram raw material primary isoamyl alcohol (content 99%) are delivered to preheater continuously by pump and are vaporized, the control input speed is about 330ml/h, the temperature of preheater is controlled at 180 ℃, enters air speed then and is in the fixed-bed reactor of netted copper/nickelalloy of 0.3/h, is heated to 430 ℃, reaction product enters the condenser cooling, after decompression distillation separates, obtain product isovaleric aldehyde 93.5 grams, through gas chromatographic analysis, content 〉=99.0% (m/m), transformation efficiency are 95.7%.
Claims (3)
1, the preparation method of isovaleric aldehyde, it is characterized in that heating primary isoamyl alcohol to vaporization, carry out the high-temperature catalytic dehydrogenation reaction with brass class catalyzer then, the gas that reaction produces obtains the product isovaleric aldehyde after condensation, separation, described brass class catalyzer is copper/zinc alloy, copper/tin alloy or copper/nickelalloy.
2, the preparation method of isovaleric aldehyde according to claim 1 is characterized in that described brass class catalyzer is netted, in the fixed-bed reactor of packing into the vaporization after primary isoamyl alcohol carry out the high-temperature catalytic dehydrogenation reaction.
3, the preparation method of isovaleric aldehyde according to claim 1 and 2, the air speed that it is characterized in that catalyzer is 0.3～0.5/h, the input speed of described primary isoamyl alcohol is 200～380ml/h, and vaporization temperature is at 160～240 ℃, and the temperature of reaction of catalytic dehydrogenation is at 400～500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031292003A CN1261399C (en) | 2003-06-11 | 2003-06-11 | Preparation method for isopentyl aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031292003A CN1261399C (en) | 2003-06-11 | 2003-06-11 | Preparation method for isopentyl aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566056A CN1566056A (en) | 2005-01-19 |
| CN1261399C true CN1261399C (en) | 2006-06-28 |
Family
ID=34469237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031292003A Expired - Lifetime CN1261399C (en) | 2003-06-11 | 2003-06-11 | Preparation method for isopentyl aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261399C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2221396A1 (en) * | 2008-12-31 | 2010-08-25 | Rohm and Haas Electronic Materials LLC | Lead-Free Tin Alloy Electroplating Compositions and Methods |
| CN104926631A (en) * | 2015-05-30 | 2015-09-23 | 吉林众鑫化工集团有限公司 | Method for preparing isoamyl aldehyde from 3-methyl-3-butenyl-1 alcohol |
| CN106008180A (en) * | 2016-06-02 | 2016-10-12 | 山东成泰化工有限公司 | Method for preparation of isovaleraldehyde from isoamyl alcohol |
| CN106117024A (en) * | 2016-06-27 | 2016-11-16 | 山东成泰化工有限公司 | A kind of preparation method of isovaleral |
| CN110627645B (en) * | 2018-06-25 | 2022-06-03 | 中国石油化工股份有限公司 | Production method for preparing glyoxylic acid ester from glycolate |
| CN111718247B (en) * | 2019-03-21 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of isovaleraldehyde |
| CN113666811B (en) * | 2021-09-13 | 2024-04-30 | 盐城市春竹香料有限公司 | Method for preparing isopentyl aldehyde by continuously catalyzing isoamyl alcohol oxidation through electrolytic silver |
| CN116162019B (en) * | 2021-11-24 | 2025-01-24 | 中国科学院大连化学物理研究所 | Method for preparing acetaldehyde by dehydrogenation of ethanol |
| CN118598735B (en) * | 2024-05-22 | 2025-11-14 | 浙江大学 | Method for preparing isopentaldehyde by oxygen-free dehydrogenation of isopentyl alcohol catalyzed by zinc oxide-based catalyst |
-
2003
- 2003-06-11 CN CNB031292003A patent/CN1261399C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1566056A (en) | 2005-01-19 |
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| C14 | Grant of patent or utility model | ||
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Owner name: SHANDONG NHU PHARMACEUTICAL CO., LTD. Free format text: FORMER OWNER: ZHEJIANG XINHECHENG CO., LTD. Effective date: 20130826 Owner name: ZHEJIANG XINHECHENG CO., LTD. Effective date: 20130826 |
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| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 312500 SHAOXING, ZHEJIANG PROVINCE TO: 261108 WEIFANG, SHANDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130826 Address after: 261108, No. 99, Chang Hai street, Binhai Economic Development Zone, Victoria Square, Shandong Patentee after: SHANDONG NHU PHARMACEUTICAL Co.,Ltd. Patentee after: ZHEJIANG NHU Co.,Ltd. Address before: 312500 No. 4 Zhenjiang North Road, Chengguan County, Zhejiang, Xinchang Patentee before: ZHEJIANG NHU Co.,Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060628 |