CN102167657A - Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst - Google Patents
Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst Download PDFInfo
- Publication number
- CN102167657A CN102167657A CN2011100719548A CN201110071954A CN102167657A CN 102167657 A CN102167657 A CN 102167657A CN 2011100719548 A CN2011100719548 A CN 2011100719548A CN 201110071954 A CN201110071954 A CN 201110071954A CN 102167657 A CN102167657 A CN 102167657A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- hydrogenation
- methacrolein
- autoclave
- alcohol
- Prior art date
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2-methylacrolein into 2-methyl allyl alcohol by using a catalytic hydrogenation method, belonging to the technical field of synthesis of organic intermediates. A catalyst used in the method is recyclable. The synthesis method comprises the following steps of: (1) adding 2-methylacrolein, a catalyst, a polymerization inhibitor and a high-boiling-point solvent into a high-pressure kettle and introducing hydrogen for reacting; (2) after reacting, exhausting excessive hydrogen and rectifying reaction liquid to obtain 2-methylacrolein; and (3) adding the 2-methylacrolein and the solvent into residual liquid in a rectifying kettle, transferring into the high-pressure kettle and undergoing a reaction for preparing 2-methylacrolein through hydrogenation to realize the recycling of the catalyst. The method has the advantages of atom economy, environmental friendliness, high yield, simple post-treatment and the like.
Description
Technical field
The invention belongs to the organic intermediate synthesis technical field, particularly a kind ofly prepare the method for metallyl alcohol by methacrolein hydrogenation, use therein catalyzer can be recycled.
Background technology
Metallyl alcohol (having another name called 2-methallyl alcohol, methacrylaldehyde or methallyl alcohol) is a kind of crucial organic intermediate, and autohemagglutination and copolyreaction can take place for itself.With the metallyl alcohol is initiator, can prepare methacrylic acid and ester thereof.In addition, metallyl alcohol can also generate with other organic acid and contain allylic ester.Therefore, metallyl alcohol is widely used in fields such as polymer monomer and tensio-active agent.
The synthetic method that is metallyl alcohol the earliest is to be raw material with propylene chlorine, and hydrolysis is prepared under alkaline condition.US2072015, US2323781, US2313767 and JP2009107949 etc. have carried out improving to this method and are perfect subsequently.At present, hydrolysis method is the topmost method of metallyl alcohol of producing, and is industrial many based on this method.Although hydrolysis method has obtained using widely, this method also exists many problems: will add a large amount of alkali and organic solvent in the hydrolytic process, hydrolysis temperature and pressure are also higher sometimes, and condition is harsh, and solvent is difficult to reclaim; Simultaneously, the growing amount of by product ether is also bigger, thereby causes the yield of target product on the low side.
Metallyl alcohol is a kind of unsaturated alcohol, as the method for preparing unsaturated alcohol, also can optionally reduce α, and aldehyde radical is to be prepared in the beta-unsaturated aldehyde.
Specifically, can be by the selective reduction chemical formula
α, the aldehyde radical of beta-unsaturated aldehyde compounds (only limit to reduce aldehyde radical) prepares.
For example, JP-B56-36176 discloses and has a kind ofly only reduced aldehyde radical with aluminium alcoholates or metal hydride selectivity prepare the method for corresponding unsaturated alcohol in the presence of Virahol.
The gas phase hydrogen transfer reactions that report is a catalyzer based on the polynary double oxide MgXYO of MgO among US2767221 and the US4731488, acrolein conversion rate and vinyl carbinol selectivity reach 90% and 92% respectively.But the temperature of reaction of this method is higher, needs to react under 300～400 ℃.Simultaneously, its alkynes Preparation of catalysts is trouble also, need at high temperature calcine and gets.
It is catalyzer that US2779801 and US2713074 adopt aluminium alcoholates, carries out the reduction reaction of unsaturated aldehyde under the homogeneous condition, and temperature, pressure are all lower, and reaction conversion ratio and selectivity all can reach more than 90%.Yet this method will adopt a large amount of aluminium alcoholates and a large amount of excessive Virahol, and wherein, aluminium alcoholates reaches 0.4 mole of starting raw material aldehyde, and Virahol is more than 20 times of starting raw material aldehyde molar weight.Therefore, this method productivity is low, and using value is little.
In order to reduce catalyst consumption, CN1190386 has reported and has added a kind of protonic acid (trifluoroacetic acid, trichoroacetic acid(TCA) or sulfonic acid etc.) that in reaction system catalyst consumption can be reduced to the 1%-25% of feed molar consumption greatly.But this catalyst system catalyst levels is still bigger, and the adding of protonic acid has simultaneously also increased production cost and isolating difficulty.
CN101069858A has reported the method that a kind of pure Al catalysts can be recycled: in the presence of aluminium alcoholates and high boiling solvent, utilize secondary alcohol that unsaturated aldehyde is carried out the reaction of homogeneous phase hydrogen transfer reduction, after reaction finishes, the reaction solution decompression is steamed, and the high boiling solvent that contains catalyzer at the bottom of the tower carries out recycle.This method is just set forth the recovery of catalyzer, and the purification of product 2-methallyl alcohol is not described.Equally, this method also adds other high boiling solvent in addition except adding the secondary alcohol in reaction system, make reaction system complicated, thereby has increased the separating difficulty of product.
Except the hydrogen transference method can be carried out the selective reduction of unsaturated aldehyde, the selective hydrogenation reduction method also can be used for preparing unsaturated alcohol.US3686333, US4072727, GB734247 and GE858247 select the Cd catalyst system for use, and as Cd-Cu, Cd-Ag, Cd-Zn etc., propenal can selective hydrogenation obtain vinyl carbinol.Report such as Yan Zhu (Angew.Chen.Int.Ed.2010,49,1295-1298), adopt nanometer Au25 (SR)
18Be catalyzer, α, beta-unsaturated aldehyde also can selective hydrogenation generate corresponding α, beta unsaturated alcohol.But its yield is lower, has only about 50%, in addition its nanometer Au25 (SR)
18Preparation of Catalyst is quite complicated, bad controlling.α in the beta-unsaturated aldehyde molecule, because the C=O bond energy is big than the C=C bond energy, makes reaction to select hydrogenation on C=O and does not destroy difficulty of C=C key that hydrogenation often generates saturated aldehyde or saturated alcohol, and is generally all relatively poor to the selectivity of unsaturated alcohol.
Summary of the invention
In order to solve the problem that occurs in the above-mentioned prior art, the invention provides a kind of method for preparing metallyl alcohol by methacrolein hydrogenation, use therein catalyzer is a transition metal composite, can be to α, and beta-unsaturated aldehyde carries out selective hydration and can be recycled.
Present method is applicable to that general formula is
(II) unsaturated aldehyde catalyzer Ru[(±)-dinaphthalene hexichol phosphorus] Cl
2Existence under, utilize hydrogen selective reduction C=O base wherein, with the preparation general formula
(I) unsaturated alcohol shown in, wherein R is hydrogen atom, halogen atom, contains the straight or branched saturated alkyl or the substituted alkyl of 1-3 carbon atom.
The hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer of the present invention can be recycled, its concrete steps are:
1. methacrolein, catalyzer, stopper and high boiling solvent are joined in the autoclave, airtight autoclave feeds hydrogen then with displaced air in autoclave, feed hydrogen after displacement is finished and carry out hydrogenation in autoclave;
2. after reaction finishes, with the reaction system cool to room temperature, discharge remaining hydrogen, open autoclave, reaction solution is forwarded in the still kettle that has rectifying column, add thermal still, reaction solution obtains the product metallyl alcohol through rectification method separation, purification;
3. after the still kettle temperature rise to 150 ℃, stop heating, and the interior raffinate of cooling still kettle is to room temperature, raffinate mainly consists of catalyzer, stopper and high boiling solvent, adopt each content of forming in the gas chromatographic analysis raffinate, add the raw material methacrolein, catalyzer, stopper makes identical with the condition of step 1 with high boiling solvent, again forward to the feed liquid of adding in the autoclave, repeating step 1,2,3, the selective hydrogenation of proceeding methacrolein prepares metallyl alcohol, thereby realize recycling of catalyzer, reusable activity of such catalysts and selectivity are basic suitable with the catalyzer that uses first.
Described catalyzer be Ru[(±)-BINAP] Cl
2, its consumption is 0.1～0.01% of a raw material methacrolein mole dosage, BINAP is a dinaphthalene hexichol phosphorus.
Described stopper is one or more among CuCl, Resorcinol, MEHQ, TBC and the TBHQ, and the stopper consumption is 0.1～0.05% of a raw material methacrolein mole dosage.
Described high boiling solvent is dimethylbenzene, N, and one or more in dinethylformamide, N,N-dimethylacetamide and the methyl-sulphoxide, high boiling solvent consumption are 5～10 times of raw material methacrolein mole dosage.
The hydrogenation pressure of described hydrogenation is 1～5MPa, and hydrogenation time is 4～10 hours, and hydrogenation temperature is 20～40 ℃.
The stage number of the rectifying column that described rectification method uses is 10～20, and the intensification scope is 30～150 ℃, and reflux ratio is 1～2.5, and fraction is collected as: 30～80 ℃, 80～100 ℃, 100～120 ℃, 120～130 ℃; Wherein in 30～80 ℃ of fractions, methacrolein content is 84～90%, in 80～100 ℃ of fractions, methacrolein content is 90～98%, in 100～120 ℃ of fractions, the content of metallyl alcohol is that the content of metallyl alcohol is 40～50% in 98～99%, 120～130 ℃ of fractions.
Described repeating step 1,2,3 operations repeat 1～10 time, and promptly catalyst recirculation is used 1～10 time.
Synthetic method provided by the invention has following advantage:
(1). adopt hydride process to prepare metallyl alcohol, have " Atom economy ", environmentally friendly, the simple advantage of aftertreatment;
(2). the catalyst levels in present method is less, and can recycle, thereby greatly reduces production cost; In addition, the catalyst recirculation using method is also very simple, is easy to realize;
(3). adopt rectification method to carry out the separation of product, can realize the purification that product is higher, and only need rectifying separation once that product content just can reach more than 98%, thereby has reduced separation costs;
(4). high boiling solvent also carries out recycle in use, thereby has reduced the cost recovery of boiling point, has saved energy consumption.
Embodiment
Come the present invention is further described below by embodiment, but protection domain is not limited only to embodiment.
Embodiment 1
1. add 70 gram methacroleins successively to 1 liter autoclave, 0.794 gram Ru[(±)-BINAP] Cl
2, 0.1 gram cuprous chloride and 530 gram dimethylbenzene, airtight autoclave feeds twice hydrogen with original air in the displacement autoclave in autoclave; Displacement is finished, the hydrogen of logical 3.5MPa in autoclave, and reacted 6 hours under 30 ℃;
2. after reaction finishes, with the reaction system cool to room temperature, discharge remaining hydrogen, open autoclave, and reaction solution forwarded in three mouthfuls of still kettles of one 1 liter, and on still kettle, load onto one 15 column plate rectifying columns are arranged, add thermal still, make the still temperature be elevated to 150 ℃ gently by room temperature, when cat head had backflow, the control reflux ratio was 1.5, collected to obtain 30～80 ℃ of fractions, 5 grams, the content of methacrolein is 85%, 80～100 ℃ of fraction 3 grams, the content of methacrolein are 95%, 100～120 ℃ of fractions, 58 grams, the content of metallyl alcohol is 98%, 120～130 ℃ of fraction 10 grams, the content of metallyl alcohol is 45%, the transformation efficiency of methacrolein is 90%, the yield of metallyl alcohol is 85%, and selectivity is 94%;
3. after the still temperature rise to 150 ℃, stop heating, and the interior raffinate of cooling still kettle is to room temperature, the composition of sampling analysis raffinate, adding raw material methacrolein, catalyzer, stopper and high boiling solvent makes identical with the condition of step 1, again forward to the feed liquid of adding in the autoclave, repeating step 1,2,3, the selective hydrogenation of proceeding methacrolein prepares metallyl alcohol, repeating step 1,2,3 operations five times, realize catalyst recirculation use five times, each charging capacity and reaction result are as shown in the table.
Table 1. catalyst recirculation is used charging capacity and reaction result
Embodiment 2
1. add 70 gram methacroleins successively to 1 liter autoclave, 0.794 gram Ru[(±)-BINAP] Cl
2, 0.05 gram cuprous chloride and 600 gram N,N-dimethylacetamide, airtight autoclave feeds twice hydrogen with original air in the displacement autoclave in autoclave; Displacement is finished, the hydrogen of logical 2.5MPa in autoclave, and reacted 8 hours under 20 ℃;
2. after reaction finishes, with the reaction system cool to room temperature, discharge remaining hydrogen, open autoclave, and reaction solution forwarded in three mouthfuls of still kettles of one 1 liter, and on still kettle, load onto one 18 column plate rectifying columns are arranged, add thermal still, make the still temperature be elevated to 150 ℃ gently by room temperature, when cat head had backflow, the control reflux ratio was 2.0, collected to obtain 30～80 ℃ of fractions, 4 grams, the content of methacrolein is 88%, 80～100 ℃ of fraction 4 grams, the content of methacrolein are 90%, 100～120 ℃ of fractions, 55 grams, the content of metallyl alcohol is 98.3%, 120～130 ℃ of fraction 8 grams, the content of metallyl alcohol is 40%, the transformation efficiency of methacrolein is 88%, the yield of metallyl alcohol is 79.4%, and selectivity is 90.3%;
3. after the still temperature rise to 150 ℃, stop heating, and the cooling still kettle in raffinate to room temperature, the composition of sampling analysis raffinate, and to wherein add 68 the gram methacroleins and 2 the gram N, the N-N,N-DIMETHYLACETAMIDE, the feed liquid of adding is forwarded in the autoclave again, repeating step 1,2, the transformation efficiency that gets methacrolein is 86.2%, the yield of metallyl alcohol is 78.1%, and selectivity is 90.6%.
Embodiment 3
1. add 140 gram methacroleins successively to 2 liters autoclave, 0.16 gram Ru[(±)-BINAP] Cl
2, 0.1 gram cuprous chloride and 1200 gram dimethylbenzene, airtight autoclave feeds twice hydrogen with original air in the displacement autoclave in autoclave; Displacement is finished, the hydrogen of logical 4.5MPa in autoclave, and reacted 10 hours under 30 ℃;
2. after reaction finishes, with the reaction system cool to room temperature, discharge remaining hydrogen, open autoclave, and reaction solution forwarded in three mouthfuls of still kettles of one 2 liters, and on still kettle, load onto one 20 column plate rectifying columns are arranged, add thermal still, make the still temperature be elevated to 150 ℃ gently by room temperature, when cat head had backflow, the control reflux ratio was 1.0, collected to obtain 30～80 ℃ of fractions, 12 grams, the content of methacrolein is 84%, 80～100 ℃ of fraction 5 grams, the content of methacrolein are 95%, 100～120 ℃ of fractions, 111 grams, the content of metallyl alcohol is 98.2%, 120～130 ℃ of fraction 18 grams, the content of metallyl alcohol is 44%, the transformation efficiency of methacrolein is 85.7%, the yield of metallyl alcohol is 81.2%, and selectivity is 94.7%;
3. after the still temperature rise to 150 ℃, stop heating, and the interior raffinate of cooling still kettle is to room temperature, the composition of sampling analysis raffinate, and, forward to the feed liquid of adding in the autoclave again to wherein adding 65 gram methacroleins and 20 gram dimethylbenzene, repeating step 1,2, the transformation efficiency that gets methacrolein is 83.8%, and the yield of metallyl alcohol is 78.1%, and selectivity is 93.2%.
Claims (7)
1. the hydrogenation synthesis method of the preparation metallyl alcohol that can be recycled of a catalyzer is characterized in that its concrete steps are:
(1) methacrolein, catalyzer, stopper and high boiling solvent are joined in the autoclave, airtight autoclave feeds hydrogen then with displaced air in autoclave, feed hydrogen after displacement is finished and carry out hydrogenation in autoclave;
(2) after reaction finishes, with the reaction system cool to room temperature, discharge remaining hydrogen, open autoclave, reaction solution is forwarded in the still kettle that has rectifying column, add thermal still, reaction solution obtains the product metallyl alcohol through rectification method separation, purification;
(3) after the still kettle temperature rise to 150 ℃, stop heating, and the interior raffinate of cooling still kettle is to room temperature, raffinate mainly consists of catalyzer, stopper and high boiling solvent, adopt each content of forming in the gas chromatographic analysis raffinate, add the raw material methacrolein, catalyzer, stopper makes identical with the condition of step (1) with high boiling solvent, again forward to the feed liquid of adding in the autoclave, repeating step (1), (2), (3), the selective hydrogenation of proceeding methacrolein prepares metallyl alcohol, thereby realize recycling of catalyzer, reusable activity of such catalysts and selectivity are basic suitable with the catalyzer that uses first.
2. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled is characterized in that, described catalyzer be Ru[(±)-BINAP] Cl
2, its consumption is 0.1～0.01% of a raw material methacrolein mole dosage, BINAP is a dinaphthalene hexichol phosphorus.
3. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled, it is characterized in that, described stopper is one or more among CuCl, Resorcinol, MEHQ, TBC and the TBHQ, and the stopper consumption is 0.1～0.05% of a raw material methacrolein mole dosage.
4. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled, it is characterized in that, described high boiling solvent is dimethylbenzene, N, dinethylformamide, N, in N-N,N-DIMETHYLACETAMIDE and the methyl-sulphoxide one or more, high boiling solvent consumption are 5～10 times of raw material methacrolein mole dosage.
5. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled is characterized in that, the hydrogenation pressure of described hydrogenation is 1～5MPa, and hydrogenation time is 4～10 hours, and hydrogenation temperature is 20～40 ℃.
6. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled, it is characterized in that, the stage number of the rectifying column that described rectification method uses is 10～20, the intensification scope is 30～150 ℃, reflux ratio is 1～2.5, and fraction is collected as: 30～80 ℃, 80～100 ℃, 100～120 ℃, 120～130 ℃; Wherein in 30～80 ℃ of fractions, methacrolein content is 84～90%, in 80～100 ℃ of fractions, methacrolein content is 90～98%, in 100～120 ℃ of fractions, the content of metallyl alcohol is that the content of metallyl alcohol is 40～50% in 98～99%, 120～130 ℃ of fractions.
7. the hydrogenation synthesis method of the preparation metallyl alcohol that a kind of catalyzer according to claim 1 can be recycled is characterized in that, described repeating step (1), (2), (3) operation repeat 1～10 time, and promptly catalyst recirculation is used 1～10 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100719548A CN102167657B (en) | 2011-03-24 | 2011-03-24 | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100719548A CN102167657B (en) | 2011-03-24 | 2011-03-24 | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167657A true CN102167657A (en) | 2011-08-31 |
| CN102167657B CN102167657B (en) | 2012-06-20 |
Family
ID=44489003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100719548A Expired - Fee Related CN102167657B (en) | 2011-03-24 | 2011-03-24 | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167657B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073392A (en) * | 2013-02-04 | 2013-05-01 | 武汉凯森化学有限公司 | Method for preparing beta-methylene phenethyl alcohol |
| CN103739445A (en) * | 2013-12-02 | 2014-04-23 | 江苏苏博特新材料股份有限公司 | Preparation method of allyl alcohol |
| CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292452A (en) * | 1978-02-01 | 1981-09-29 | Standard Oil Company (Indiana) | Rhodium-catalyzed hydrogenation of unsaturated aldehydes to unsaturated alcohols |
| JP2001354607A (en) * | 2000-06-08 | 2001-12-25 | Daicel Chem Ind Ltd | Method of producing unsaturated alcohol |
| CN101069858A (en) * | 2007-02-09 | 2007-11-14 | 上海华谊丙烯酸有限公司 | Method for recovering aluminium alcoholate catalyst in preparation of non-saturated alcohol by transfer reduction of non-saturated aldehydo-hydrogen |
-
2011
- 2011-03-24 CN CN2011100719548A patent/CN102167657B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292452A (en) * | 1978-02-01 | 1981-09-29 | Standard Oil Company (Indiana) | Rhodium-catalyzed hydrogenation of unsaturated aldehydes to unsaturated alcohols |
| JP2001354607A (en) * | 2000-06-08 | 2001-12-25 | Daicel Chem Ind Ltd | Method of producing unsaturated alcohol |
| CN101069858A (en) * | 2007-02-09 | 2007-11-14 | 上海华谊丙烯酸有限公司 | Method for recovering aluminium alcoholate catalyst in preparation of non-saturated alcohol by transfer reduction of non-saturated aldehydo-hydrogen |
Non-Patent Citations (1)
| Title |
|---|
| 《分子催化》 19950630 王祥智，陈华，黎耀忠，胡家元，李贤均 两相催化体系中alpha，beta－不饱和醛的选择性加氢反应研究Ⅰ．水溶性钌－膦配合物催化肉桂醛的加氢性能 , 第03期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073392A (en) * | 2013-02-04 | 2013-05-01 | 武汉凯森化学有限公司 | Method for preparing beta-methylene phenethyl alcohol |
| CN103073392B (en) * | 2013-02-04 | 2014-12-17 | 武汉凯森化学有限公司 | Method for preparing beta-methylene phenethyl alcohol |
| CN103739445A (en) * | 2013-12-02 | 2014-04-23 | 江苏苏博特新材料股份有限公司 | Preparation method of allyl alcohol |
| CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
| CN103755523B (en) * | 2013-12-02 | 2016-02-03 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of 2-methallyl alcohol |
| CN103739445B (en) * | 2013-12-02 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of allyl alcohol |
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
| CN106278814B (en) * | 2015-06-10 | 2019-04-23 | 万华化学集团股份有限公司 | Method that is a kind of while preparing methallyl alcohol and cyclododecanone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167657B (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20150056645A (en) | Method and device for coproducing cyclohexanol and alkanol | |
| CN102701977A (en) | Continuous synthesis method for methyl methoxyacetate | |
| CN103755523B (en) | A kind of preparation method of 2-methallyl alcohol | |
| CN102167657B (en) | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst | |
| CN101659597A (en) | Method for preparing Guerbet alcohol | |
| CN104592030A (en) | Method for synthesizing phthalate compounds | |
| CN102020526B (en) | Method for preparing isobutene by adopting tertiary butanol | |
| CN103588618B (en) | Ritalin hydrogenation produces reactive distillation method and the device of ethanol | |
| CN114702375A (en) | Separation system and method for ethanol-to-acetaldehyde product | |
| CN105384616A (en) | Synthetic method for methoxyacetone | |
| CN101074187B (en) | Production of o-phenylphenol | |
| CN104529730A (en) | Method for preparing 3-pentanone by using 2-pentene | |
| CN105439792B (en) | The method of the refined propylene of recovery | |
| CN103864587A (en) | Method for synthesizing 2-ethyl-2-hexenal | |
| CN102976910A (en) | Environment-friendly and simple preparation method for synthesizing isophorone from acetone | |
| CN101747156A (en) | New method for preparing 2,4-ditert-pentyl-phenol | |
| CN113880689A (en) | Preparation method of 3-methyl-1, 5-pentanediol | |
| CN104447255A (en) | Method for preparing 2-pentanone from 2-amylene | |
| CN107952479B (en) | Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst | |
| CN102180771A (en) | Preparation method for 3-methyl-3-butene-1-alcohol | |
| CN203582764U (en) | Production device for preparing ethanol by hydrogenating methyl acetate | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation | |
| CN101531574A (en) | Method for preparing 3,4,5-trimethoxy toluene | |
| CN203700237U (en) | Reaction system for synthesizing isobutyl isobutyrate through isobutanol | |
| CN117886693B (en) | Synthesis method of 3-ethoxyethyl acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120620 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |