CN102503772A - Method for producing 2-methyl-3-butene-2-ol - Google Patents
Method for producing 2-methyl-3-butene-2-ol Download PDFInfo
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- CN102503772A CN102503772A CN2011103069039A CN201110306903A CN102503772A CN 102503772 A CN102503772 A CN 102503772A CN 2011103069039 A CN2011103069039 A CN 2011103069039A CN 201110306903 A CN201110306903 A CN 201110306903A CN 102503772 A CN102503772 A CN 102503772A
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Abstract
The invention relates to a method for producing 2-methyl-3-butene-2-ol. The method comprises the step of: passing 2-methyl-3-butyne-2-ol material through a catalyst bed of a fixed bed in the presence of hydrogen for hydrogenation reaction, wherein the bulk liquid hourly space velocity is controlled to be 1.0-5.0 hr<->, the pressure is 0.5-2.0 MPa, the reaction temperature is controlled to be 20-60 DEG C, the molar ratio of hydrogen to 2-methyl-3-butyne-2-ol is (1.2-1.5):1, 0.0005-0.0010% of dimethyl disulfide is added to 2-methyl-3-butyne-2-ol, and the catalyst is a supported catalyst with Pd as an active ingredient and Al2O3 as a carrier. Compared with the prior art, the method has the advantages that trace dimethyl disulfide is added to the 2-methyl-3-butyne-2-ol raw material during hydrogenation, and both the conversion rate and selectivity of hydrogenation reaction are approximate to 100% on the premise that other hydrogenation conditions are not changed.
Description
Technical field
The present invention relates to the working method of a kind of 2-methyl-3-butene-2-alcohol, particularly with 2-methyl-3-butyne-2-alcohol at Pd/Al
2O
3Catalyzer exists down, prepares the method for 2-methyl-3-butene-2-alcohol through selective hydrogenation.
Background technology
2-methyl-3-butene-2-alcohol (methyl butene alcohol) is a kind of important fine-chemical intermediate; Except the raw material that can be used for synthetic DV-chrysanthemumic acid or chrysanthemum monocarboxylate; Also be used to produce Sulcatone, different vegetable alcohol (VE main intermediate), DV chrysanthemumic acid, synthesise vitamins A, carrotenoid, terpenes series spices midbody; The additive that also is used for bath article, it still prevents and treats the major ingredient of injurious forest-insect sexual attractant in addition.
The production of methyl butene alcohol mainly is to be raw material with acetone and acetylene at present, and acetylene and acetone are changed into 2-methyl-3-butyne-2-alcohol under the basic catalyst effect, and is pure through selective hydrogenation generation methyl butene again.At present mainly use Powdered Lindlar (Pd-Pb/CaCO for the selective hydrogenation of 2-methyl-3-butyne-2-alcohol
3) catalyzer, and add the effect that an amount of quinoline or pyridine or trimeric cyanamide improve hydrogenation.General hydrogenation conversion is 100%, and the selectivity of methyl butene alcohol is 96～98%.Hydrogenation reaction is carried out in having the autoclave of stirring usually, and after hydrogenation was accomplished, needing granularity was that 800～1000 purpose Lindlar catalyzer separate with hydrogenation liquid, and the catalyst recycle of recovery is applied mechanically.The comparatively loaded down with trivial details and catalyzer of hydrogenation technique is easy to loss, and hydrogenation can not carry out continuously.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of method of producing 2-methyl-3-butene-2-alcohol through selective hydrogenation to be provided, and hydrogenation process adopts Pd/Al
2O
3Catalyzer carries out the hydrogenation of 2-methyl-3-butyne-2-alcohol continuously, has simplified hydrogenation technique.
The object of the invention can be realized through following technical scheme:
A kind of working method of methyl butene alcohol, this method comprises carries out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen.The volume liquid hourly space velocity is controlled to be 1.0～5.0hr
-1System pressure is controlled to be 0.5～2.0MPa; The reaction-ure feeding temperature is controlled to be 20～60 ℃, and the molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is (1.2～1.5): 1, add 0.005～0.010 ‰ NSC 9370 in 2-methyl-3-butyne-2-alcohol material.Catalyzer is to be active constituent and with Al with Pd
2O
3Be the loaded catalyst of carrier, the weight percentage of Pd is 0.3～0.5% in the catalyzer.
Above-mentioned described volume liquid hourly space velocity control is preferably 2.0～3.0hr
-1System pressure is preferably 0.6～1.0MPa; Temperature of reaction is preferably 30～50 ℃; The molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is (1.3～1.4): 1; The content of NSC 9370 is preferably 0.006～0.008 ‰ in 2-methyl-3-butyne-2-alcohol material.
The Pd/Al that adopts
2O
3Catalyzer is classical hydrogenation catalyst, and there are two kinds of hydrogenation activity positions in this catalyzer, but the hydrogenation of high reactivity position catalysis monoolefine wherein, but the hydrogenation of middle low activity position catalysis diolefin or alkynes.Behind catalyzer absorption NSC 9370, after hydrogenation activity had been lost in the high reactivity position, middle low activity position still had hydrogenation activity.
The absorption of NSC 9370 on the catalyst activity position is the major cause that influences the catalyst hydrogenation performance; Usually absorption can be divided into two kinds of physical adsorption and chemisorption; Physical adsorption is that sulfide is attached to the hydrogenation activity that the catalyst activity position reduces catalyzer with Van der Waals force; And chemisorption is the strong interaction between sulfide and the catalyst activity position, and the former can cause the reversibility of catalyzer, temporary inactivation, and the latter is irreversible permanent inactivation.
Essence of the present invention is to use Pd/Al
2O
3During catalyzer, in hydrogenating materials, add an amount of NSC 9370.The contriver is through discovering, NSC 9370 is at Pd/Al
2O
3The catalyst surface adsorptive power is stronger, can poison activity of such catalysts, improves the selectivity of hydrogenation.
Advantage compared with prior art of the present invention very significantly; The technology of hydrogenation step is very simple; Just when hydrogenation, micro-NSC 9370 is added in raw material 2-methyl-3-butyne-2-alcohol; Under the constant prerequisite of other hydroconversion condition, transformation efficiency and the selectivity that can make hydrogenation are all near 100%.
Embodiment
Embodiment below by concrete is further described the present invention, because with respect to the prior art improvement that focuses on hydrogenation step of the present invention, all the other and prior art are basic identical, so embodiment will pay attention to the description to hydrogenation step.In an embodiment, the definition of the transformation efficiency of volume of liquid air speed, hydrogenation reaction and selectivity is respectively:
Embodiment 1～10
Hydrogenation reaction is carried out in stainless steel tubular type reactor drum, and reactor drum is that one ruler cun is the stainless steel tubular type reactor drum of φ 25mm * 1000mm.Filling 100ml catalyzer in the reaction tubes, catalyzer are to be active constituent with Pd and to be the spherical supported type catalyzer of carrier with Al2O3, and its particle diameter is 0.3～0.5mm, and the weight percentage of Pd is 0.35% in the catalyzer, reactor bottom filling inert ceramic balls.Need before the charging live catalyst to be carried out activation with hydrogen.
The methylbutynol that adds an amount of NSC 9370 is sent into hydrogenator with the speed of setting by the top with pump after preheating, hydrogen gets in the reactor drum through gas distributor, and hydrogenating materials is mixed back entering beds and carried out hydrogenation reaction with hydrogen.Hydrogenation products gets into a gas-liquid separator by the hydrogenator bottom, and liquid phase material gets into product storage tank.The unreacting hydrogen of being told by gas-liquid separator gets into wet gas meter metering back emptying after the variable valve decompression, or compression back Returning reacting system.Hydrogenation conditions that each embodiment is concrete and hydrogenation result see table 1 and table 2.
Table 1.
Raw material is a methylbutynol; DMDS is a NSC 9370.
Table 2.
Embodiment 11
A kind of method of producing 2-methyl-3-butene-2-alcohol; This method is carried out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen; Control reaction temperature is controlled to be 20 ℃; The molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is 1.2: 1, and the adding weight percentage is 0.005 ‰ NSC 9370 in 2-methyl-3-butyne-2-alcohol material, and the volume liquid hourly space velocity of fixed bed is controlled to be 1.0hr
-1, pressure is 0.5MPa, the catalyzer that catalytic bed adopts is for being active constituent with Pd, with Al
2O
3Be the loaded catalyst of carrier, the weight percentage of Pd is 0.3%, the synthetic 2-methyl-3-butene-2-alcohol that obtains.
Embodiment 12
A kind of method of producing 2-methyl-3-butene-2-alcohol; This method is carried out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen; Control reaction temperature is controlled to be 30 ℃; The molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is 1.3: 1, and the adding weight percentage is 0.006 ‰ NSC 9370 in 2-methyl-3-butyne-2-alcohol material, and the volume liquid hourly space velocity of fixed bed is controlled to be 2.0hr
-1, pressure is 0.6MPa, the catalyzer that catalytic bed adopts is for being active constituent with Pd, with Al
2O
3Be the loaded catalyst of carrier, the weight percentage of Pd is 0.4%, the synthetic 2-methyl-3-butene-2-alcohol that obtains.
Embodiment 13
A kind of method of producing 2-methyl-3-butene-2-alcohol; This method is carried out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen; Control reaction temperature is controlled to be 50 ℃; The molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is 1.4: 1, and the adding weight percentage is 0.008 ‰ NSC 9370 in 2-methyl-3-butyne-2-alcohol material, and the volume liquid hourly space velocity of fixed bed is controlled to be 3.0hr
-1, pressure is 1.0MPa, the catalyzer that catalytic bed adopts is for being active constituent with Pd, with Al
2O
3Be the loaded catalyst of carrier, the weight percentage of Pd is 0.4%, the synthetic 2-methyl-3-butene-2-alcohol that obtains.
Embodiment 14
A kind of method of producing 2-methyl-3-butene-2-alcohol; This method is carried out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen; Control reaction temperature is controlled to be 60 ℃; The molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is 1.5: 1, and the adding weight percentage is 0.010 ‰ NSC 9370 in 2-methyl-3-butyne-2-alcohol material, and the volume liquid hourly space velocity of fixed bed is controlled to be 5.0hr
-1, pressure is 2.0MPa, the catalyzer that catalytic bed adopts is for being active constituent with Pd, with Al
2O
3Be the loaded catalyst of carrier, the weight percentage of Pd is 0.5%, the synthetic 2-methyl-3-butene-2-alcohol that obtains.
Claims (8)
1. method of producing 2-methyl-3-butene-2-alcohol; It is characterized in that; This method is carried out hydrogenation reaction through the fixed bed catalyst bed with 2-methyl-3-butyne-2-alcohol material in the presence of hydrogen; Control reaction temperature is controlled to be 20～60 ℃, and the molar ratio of hydrogen and 2-methyl-3-butyne-2-alcohol material is (1.2～1.5): 1, and the volume liquid hourly space velocity of fixed bed is controlled to be 1.0～5.0hr
-1, pressure is 0.5～2.0MPa, the catalyzer that catalytic bed adopts is for being active constituent with Pd, with Al
2O
3Be the loaded catalyst of carrier, the synthetic 2-methyl-3-butene-2-alcohol that obtains.
2. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that described volume liquid hourly space velocity is 2.0～3.0hr
-1
3. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that described pressure is 0.6～1.0MPa.
4. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that described temperature of reaction is 30～50 ℃.
5. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that the molar ratio of described hydrogen and 2-methyl-3-butyne-2-alcohol material is (1.3～1.4): 1.
6. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that, the adding weight percentage is 0.005～0.010 ‰ NSC 9370 in described 2-methyl-3-butyne-2-alcohol material.
7. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that, the adding weight percentage is 0.006～0.008 ‰ NSC 9370 in described 2-methyl-3-butyne-2-alcohol material.
8. a kind of method of producing 2-methyl-3-butene-2-alcohol according to claim 1 is characterized in that the weight percentage of Pd is 0.3～0.5% in the described catalyzer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2734459C1 (en) * | 2020-03-18 | 2020-10-16 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет" (ФГБОУ ВО "ИГУ") | Method of hydrogenating acetylenic alcohols (versions) |
| CN113874340A (en) * | 2019-05-27 | 2021-12-31 | 帝斯曼知识产权资产管理有限公司 | Selective hydrogenation of alkynes to alkenes in the presence of phosphorus compounds and organic sulfur compounds |
| CN115403448A (en) * | 2021-05-27 | 2022-11-29 | 宿迁科思化学有限公司 | Isopentenol and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616733A (en) * | 2007-02-19 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | Based on the catalyst that is used for alkynol hydrogenation that is coated with through the zinc oxide film of palladium nano-particles dipping through sintered metal fiber |
| CN102131578A (en) * | 2008-08-20 | 2011-07-20 | 帝斯曼知识产权资产管理有限公司 | Novel selective hydrogenation catalyst comprising palladium on porous silica glass and the use thereof |
-
2011
- 2011-10-11 CN CN2011103069039A patent/CN102503772A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616733A (en) * | 2007-02-19 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | Based on the catalyst that is used for alkynol hydrogenation that is coated with through the zinc oxide film of palladium nano-particles dipping through sintered metal fiber |
| CN102131578A (en) * | 2008-08-20 | 2011-07-20 | 帝斯曼知识产权资产管理有限公司 | Novel selective hydrogenation catalyst comprising palladium on porous silica glass and the use thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113874340A (en) * | 2019-05-27 | 2021-12-31 | 帝斯曼知识产权资产管理有限公司 | Selective hydrogenation of alkynes to alkenes in the presence of phosphorus compounds and organic sulfur compounds |
| RU2734459C1 (en) * | 2020-03-18 | 2020-10-16 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет" (ФГБОУ ВО "ИГУ") | Method of hydrogenating acetylenic alcohols (versions) |
| CN115403448A (en) * | 2021-05-27 | 2022-11-29 | 宿迁科思化学有限公司 | Isopentenol and preparation method thereof |
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Application publication date: 20120620 |