CN1145892A - Synthesis process of 2,5-dimethyl-2,4-hexadiene - Google Patents
Synthesis process of 2,5-dimethyl-2,4-hexadiene Download PDFInfo
- Publication number
- CN1145892A CN1145892A CN 95112007 CN95112007A CN1145892A CN 1145892 A CN1145892 A CN 1145892A CN 95112007 CN95112007 CN 95112007 CN 95112007 A CN95112007 A CN 95112007A CN 1145892 A CN1145892 A CN 1145892A
- Authority
- CN
- China
- Prior art keywords
- hexadiene
- dimethyl
- component
- reaction
- acid
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
Abstract
The synthesis process features that isobutylene, or tertiary butanol, or methyl tertbutyl ether or their mixture is condensated directly with isobutyraldehyde at the conditions of 60-500 deg.C temp, 0.1-5 MPa pressure, 0.1-10/hr weight space velocity, with the weight ratio of isobutylene to isobutyraldehyde being 1-10. It is simple, safe and reliable and has high yield.
Description
The present invention relates to a kind of production 2,5-dimethyl 2, the novel process process of 4-hexadiene and niobic acid and wolframic acid System Catalyst, be raw material promptly with iso-butylene (or trimethyl carbinol) and isobutyric aldehyde, under niobic acid or wolframic acid or other solid heteropoly acid catalyst action, but high reactivity, highly selective preparation 2,5-dimethyl 2, the 4-hexadiene.
Pyrethroid pesticide is the novel agrochemical of recent development in the world; generally have efficient; low toxicity, residual advantage such as low is widely used in agricultural; forestry; fields such as material protection and family's mosquito proof, and 2,2; 5-dimethyl 2,4-hexadiene are the body materials of synthetic multiple pyrethroid pesticide intermediate first chrysanthemumic acid.A large amount of both at home and abroad at present first chrysanthemum esters (Cyphenothrin) that use, esbiothrin (Allethrin), PH (Furamethrin), (Methothrin), Tetramethrins (Tetramethrin) etc. all be to be the acid constituents synthetic with first chrysanthemumic acid, and first chrysanthemumic acid are by 2,5-dimethyl 2,4-hexadiene and glycine ester make by cyclopropanization reaction.Therefore, 2,5-dimethyl 2, synthesizing in the production of pyrethroid pesticide of 4-hexadiene is significant.
Because 2,5-dimethyl 2, the 4-hexadiene is fine chemicals intermediates such as very important agricultural chemicals, medicine, and people pay attention to its production and exploitation always for a long time, because the cost problem, mostly be confined to the synthetic (J.C.S.Chem.Commun.Vol.9 in laboratory, P617,1984), for example, method preparation 2 with isobutene oligomerisation, 5-dimethyl 2, the 4-hexadiene just can obtain 2 but also need to carry out isomerization, 5-dimethyl 2, the 4-hexadiene, and, cause 2 with a large amount of superpolymer by products generations, 5-dimethyl 2, the yield of 4-hexadiene is very low.
Major industry at present produces 2,5-dimethyl 2, and the method for 4-hexadiene is the acetylene acetone method.It is acetylene and acetone prepared in reaction 2 under high pressure, 5-dimethyl 2, the 5-hexadiene obtains 2 through dehydration and isomerization reaction again, 5-dimethyl 2,4-hexadiene, yet this complex technical process, dangerous big (acetylene explosive), by-product is many, 2,5-dimethyl 2, the yield of 4-hexadiene also very low (＜30%).
The object of the present invention is to provide a kind of technological process simple, operational safety is reliable and 2,5-dimethyl 2, and 4-4 hexadiene yield height is suitable for 2 of suitability for industrialized production, 5-dimethyl 2, the synthetic method of 4-hexadiene, and catalyst system therefor.
The invention provides a kind of Synthetic 2,5-dimethyl 2, the process of 4-hexadiene is characterized in that: adopt iso-butylene, or the trimethyl carbinol, or methyl tertiary butyl ether or its mixture, with isobutyric aldehyde as raw material, under catalyst action, carry out condensation reaction, direct production 2,5-dimethyl 2,4-hexadiene.
The reaction conditions of this reaction is as follows:
Temperature of reaction 60-500 ℃
Reaction pressure 0.1-5MPa
Weight space velocity 0.1-10h
-1
Iso-butylene/isobutyric aldehyde (weight ratio)=1-10
Preferable reaction conditions is:
Temperature of reaction: 200-350 ℃
Reaction pressure: 0.5-5MPa
Weight space velocity: 0.5-5h
-1
Iso-butylene/isobutyric aldehyde=1-6
The present invention also provides above-mentioned catalyst for reaction, and this catalyzer is active ingredient (component 1) with niobic acid or wolframic acid, can add Fe, Al, the Cu-inorganic salt are made catalyst adjuvant (component 2), and weight ratio is a component 1: component 2=100: 0.1-100, also can add solid acid such as Al
2O
3, ZrO
2, TiO
2Deng, or zeolite molecular sieve to make auxiliary agent (component 3) weight ratio be component 1: component 3=100: 0.1-100; Or: component 1: component 2: component 3=100: 0.1-100: 0.1-100
Above-mentioned catalyzer can be by following method preparation
A: with niobic acid in 100-300 ℃ of roasting or wolframic acid in 500-600 ℃ of calcination process, can adopt phosphoric acid or sulfuric acid or nitric acid pretreatment before the roasting.
B: with r-Al
2O
3Or FeSO
4Or CuSO
4Or Al
2(SO
4)
3500-600 ℃ of calcination process.
C: it is even to carry out mechanically mixing by required component, carries out mechanical compression molding then or adds the binding agent moulding.
Catalyzer of the present invention can be at continuous fixed bed reactor, at temperature of reaction 100-500 ℃, and reaction pressure 0.5-5MPa, charging air speed (W) 0.5-10h
-1Down operation of reaction conditions.
Synthetic 2 of the present invention, 5-dimethyl 2, the novel process process and the catalyst system of 4-hexadiene have following characteristics: raw material conveniently is easy to get, adopt heterogeneous catalysis technology, with nitrogen or other rare gas element or iso-butylene stopping reaction pressure, adopt the circulation technology flow process to improve transformation efficiency and 2,5-dimethyl 2, the yield of 4-hexadiene, catalyzer of the present invention has good selectivity and very high catalytic activity, thereby have higher product yield, content of the present invention described in detail below by example:
Accompanying drawing 1 is a Synthetic 2,5-dimethyl 2,4-hexadiene process flow sheet
Embodiment 1: the preparation of niobic acid system composite catalyst A
Niobic acid 15 is restrained in 10%H
3PO
4Or 10%H
2SO
4Or after soaking 3hr among its mixing solutions 30ml, be neutral with deionized water rinsing to PH, 300 ℃ of roasting 5hr are again with TiO
25 grams (550 ℃ of roasting 6hr), r-Al
2O
35 grams (500 ℃ of roasting 5hr) add FeSo
4Or CuSO
4Mechanically mixing compression molding or the moulding of interpolation binding agent obtain catalyst A.
Embodiment 2: the preparation of niobic acid system composite catalyst B
With niobic acid 15 gram (250 ℃ of roasting 5hr) and CuSO
4(500 ℃, 5hr) even compression molding of mechanically mixing or the moulding of interpolation binding agent obtain catalyst B to 10 grams.
Embodiment 3: the preparation of niobic acid system composite catalyst C
With niobic acid 15 grams (250 ℃ of roasting 6hr) and Si-Al zeolite molecular sieve 5 gram (500 ℃ of roasting 4hr) and CuSO
42 grams (500 ℃ of roasting 5hr), FeSo
42 grams (500 ℃ of roasting 5hr), r-Al
2O
32 gram (500 ℃ of roasting 5hr) even compression moldings of mechanically mixing or the moulding of interpolation binding agent obtain catalyzer C.
Embodiment 4: the preparation of wolframic acid system composite catalyst D
With wolframic acid 15 gram (500 ℃ of roasting 6hr) and TiO
210 grams (550 ℃ of roasting 6hr), r-Al
2O
35 gram (800 ℃ of roasting 5hr) even compression moldings of mechanically mixing or the moulding of interpolation binding agent obtain catalyzer D.
Embodiment 5: the preparation of wolframic acid system composite catalyst E
With wolframic acid 15 gram (500 ℃ of roasting 6hr) and TiO
25 grams (550 ℃ of roasting 6hr), ZrO
25 gram (500 ℃ of roasting 5hr) even compression moldings of mechanically mixing or the moulding of interpolation binding agent obtain catalyzer E.
The preparation of embodiment 6 niobic acid System Catalyst F
250 ℃ of roasts 6 hours, the ball milling moulding obtained catalyzer F with niobic acid 15 gram.
Embodiment 7: the trimethyl carbinol and isobutyric aldehyde reaction Synthetic 2,5-dimethyl 2,4-hexadiene experiment 1
Technical process is as figure (1), with reaction raw materials (1) in voltage stabilizing (2) system of nitrogen or iso-butylene or other rare gas element, pump into flowable state fixed-bed reactor (3) and carry out building-up reactions, reaction product isolates 2 through separator (4), 5-dimethyl 2,4-hexadiene product (5) and unreacted iso-butylene (6) and aldehyde (7), unreacted iso-butylene (6) and isobutyric aldehyde (7) the recycle pump dynamic fixing bed bioreactor (3) that becomes a mandarin is reacted again, Synthetic 2,5-dimethyl 2,4-hexadiene.The catalyst A of the above-mentioned development of filling 10ml on continuous fixed bed reactor.2.0MPa 250 ℃, weight space velocity is 5h
-1Reaction conditions under, carry out condensation reaction (its molecular ratio is 4: the 1) Synthetic 2 of iso-butylene (trimethyl carbinol) and isobutyric aldehyde, 5-dimethyl 2 with the N2 voltage stabilizing, the 4-hexadiene, the per pass conversion of isobutyric aldehyde reaches 40.5%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 78%.
Embodiment 8: iso-butylene and isobutyric aldehyde prepared in reaction 2,5-dimethyl 2,4-hexadiene experiment 2
The 80 gram trimethyl carbinols and 20 restrain the continuous fixed bed reactor that pumps into the catalyst B that the above-mentioned development of 10ml is housed after isobutyric aldehydes mix.Reaction conditions is, 240 ℃, and 2.0MPa, weight space velocity is 5h-1, uses N
2Voltage stabilizing, circulating reaction.The transformation efficiency of isobutyric aldehyde reaches 86%, 2,5-dimethyl 2, and the selectivity of 4-hexadiene reaches 81%.
Embodiment 9: iso-butylene (trimethyl carbinol) and isobutyric aldehyde prepared in reaction 2,5-dimethyl 2,4-hexadiene experiment 3
The 80 gram trimethyl carbinols pump into a continuous fixed bed reactor 1 that the 10ml catalyst A is housed, and weight space velocity is 4h
-1, the water of generation is with cold and collect, and the iso-butylene of generation pumps into reactor 2 simultaneously by a continuous fixed bed reactor 2.20ml isobutyric aldehyde that 10ml catalyzer C is housed again, and weight space velocity is 1h
-1, reaction conditions is 260 ℃, 2MPa N
2Voltage stabilizing, circulating reaction, the transformation efficiency of isobutyric aldehyde reaches 90%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 81%.
Embodiment 10 iso-butylenes (methyl tertiary butyl ether) and isobutyric aldehyde reaction Synthetic 2,5-dimethyl 2,4-hexadiene experiment 4
100 gram methyl tertiary butyl ethers pump into a continuous fixed bed reactor 1 that the 10ml catalyst A is housed, and weight space velocity is 4h
-1, the water of generation receives with cold well, and the iso-butylene of generation by a continuous fixed bed reactor 2 that catalyzer C is housed, pumps into reactor 2 with the 20ml isobutyric aldehyde more simultaneously, and weight space velocity is 1h
-1, reaction conditions is 250 ℃, 2MPa N
2Voltage stabilizing, circulating reaction, the per pass conversion of isobutyric aldehyde reaches 89%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 80%.
Embodiment 11 ripple butanols and isobutyric aldehyde reaction Synthetic 2,5-dimethyl 2,4-hexadiene experiment 5
The 80 gram trimethyl carbinols and 20 restrain and to pump into a continuous fixed bed reactor that the catalyzer D of above-mentioned development is housed behind the isobutyric aldehyde uniform mixing.Reaction conditions is 245 ℃, 3MPa N
2Voltage stabilizing, circulating reaction, the per pass conversion of isobutyric aldehyde reaches 80%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 70%.
Embodiment 12 trimethyl carbinols and isobutyric aldehyde reaction Synthetic 2,5-dimethyl 2,4-hexadiene experiment 6
Adopt reaction conditions and the catalyzer loading amount identical, catalyzer E is carried out the trimethyl carbinol and isobutyric aldehyde prepared in reaction 2,5-dimethyl 2 with above-mentioned example 10, the performance evaluation of 4-hexadiene, the transformation efficiency of its isobutyric aldehyde reaches 79%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 72%.
Embodiment 13 trimethyl carbinols and isobutyric aldehyde reaction Synthetic 2,5-dimethyl 2,4-hexadiene experiment 7
Adopt reaction conditions and the catalyzer loading amount identical, catalyzer F is carried out the trimethyl carbinol and isobutyric aldehyde prepared in reaction 2,5-dimethyl 2 with above-mentioned example 10, the performance evaluation of 4-hexadiene, the transformation efficiency of its isobutyric aldehyde reaches 79%, 2,5-dimethyl 2, the selectivity of 4-hexadiene reaches 62%.
Claims (8)
1. Synthetic 2,5-dimethyl 2, the process of 4-hexadiene is characterized in that: adopt iso-butylene, or the trimethyl carbinol, or methyl tertiary butyl ether or its mixture, with isobutyric aldehyde as raw material, under catalyst action, carry out condensation reaction, direct production 2,5-dimethyl 2,4-hexadiene.
2. press the described Synthetic 2 of claim 1,5-dimethyl 2, the process of 4-hexadiene is characterized in that: reaction conditions is as follows:
Temperature of reaction 60-500 ℃
Reaction pressure 0.1-5MPa
Weight space velocity 0.1-10h
-1
Iso-butylene/isobutyric aldehyde (weight ratio)=1-10
3. press the described Synthetic 2 of claim 2,5-dimethyl 2,4-hexadiene process is characterized in that: preferable reaction conditions is:
Temperature of reaction: 200-350 ℃
Reaction pressure: 0.5-5MPa
Weight space velocity: 0.5-5h
-1
Iso-butylene/isobutyric aldehyde=1-6
4. described Synthetic 2 of claim 1,5-dimethyl 2,4-hexadiene process catalyzer is characterized in that: this catalyzer is active ingredient (component 1) with niobic acid or wolframic acid
5. press the described Synthetic 2 of claim 4,5-dimethyl 2,4-hexadiene process catalyzer is characterized in that: can add Fe, Al, the inorganic salt of Cu make catalyst adjuvant (component 2), and weight ratio is a component 1: component 2=100: 0.1-100
6. press the described Synthetic 2 of claim 4,5-dimethyl 2,4-hexadiene process catalyzer is characterized in that: can add solid acid such as Al
2O
3, ZrO
2, TiO
2Deng, or zeolite molecular sieve to make auxiliary agent (component 3) weight ratio be component 1: component 3=100: 0.1-100
7. press the described Synthetic 2 of claim 5,5-dimethyl 2,4-hexadiene process catalyzer is characterized in that: can add solid acid such as Al
2O
3, ZrO
2, TiO
2Deng, or zeolite molecular sieve is made auxiliary agent (component 3)
Component 1: component 2: component 3=100: 0.1-100: 0.1-100
8. claim 4,5,6,7 described Synthetic 2s, 5-dimethyl 2,4-hexadiene process is with the method for catalyzer, and it is characterized in that: preparation process is as follows:
A: with niobic acid in 100-300 ℃ of roasting or wolframic acid in 500-600 ℃ of calcination process, can adopt phosphoric acid or sulfuric acid or nitric acid pretreatment before the roasting;
B: with r-Al
2O
3Or FeSO
4Or CuSO
4Or Al
2(SO
4)
3500-600 ℃ of calcination process;
C: it is even to carry out mechanically mixing by required component, carries out mechanical compression molding then or adds the binding agent moulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95112007 CN1145892A (en) | 1995-09-20 | 1995-09-20 | Synthesis process of 2,5-dimethyl-2,4-hexadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95112007 CN1145892A (en) | 1995-09-20 | 1995-09-20 | Synthesis process of 2,5-dimethyl-2,4-hexadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1145892A true CN1145892A (en) | 1997-03-26 |
Family
ID=5079233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95112007 Pending CN1145892A (en) | 1995-09-20 | 1995-09-20 | Synthesis process of 2,5-dimethyl-2,4-hexadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1145892A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335169C (en) * | 2004-07-12 | 2007-09-05 | 上海华谊丙烯酸有限公司 | Niobium catalyst for dehydropyran derivative hydrolysis and its use |
| CN103638955A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN106831293A (en) * | 2016-12-08 | 2017-06-13 | 大连九信精细化工有限公司 | A kind of recoverying and utilizing method of the hexadiene isomers of 2,5 dimethyl 2,4 |
| CN115477568A (en) * | 2022-09-20 | 2022-12-16 | 润泰化学（泰兴）有限公司 | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid |
-
1995
- 1995-09-20 CN CN 95112007 patent/CN1145892A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335169C (en) * | 2004-07-12 | 2007-09-05 | 上海华谊丙烯酸有限公司 | Niobium catalyst for dehydropyran derivative hydrolysis and its use |
| CN103638955A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN103638955B (en) * | 2013-12-17 | 2016-06-01 | 中国科学院长春应用化学研究所 | The preparation method of a kind of solid acid catalyst, its preparation method and double olefin compound |
| CN106831293A (en) * | 2016-12-08 | 2017-06-13 | 大连九信精细化工有限公司 | A kind of recoverying and utilizing method of the hexadiene isomers of 2,5 dimethyl 2,4 |
| CN115477568A (en) * | 2022-09-20 | 2022-12-16 | 润泰化学（泰兴）有限公司 | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1303048C (en) | Process for preparing dimethylether from methanol | |
| Le Van Mao et al. | The bioethanol-to-ethylene (BETE) process | |
| CN1083415A (en) | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and building-up reactions | |
| CN1771224A (en) | Process for the preparation of alkanediol | |
| CN1114495C (en) | Process for preparing composite catalyst and its application | |
| CN1080585C (en) | Photocatalyst, method for preparing the same, and production of hydrogen using the same | |
| CN1101265C (en) | Solid acid catalyst containing heteropoly acid and its preparing process | |
| CN1145892A (en) | Synthesis process of 2,5-dimethyl-2,4-hexadiene | |
| CN1268505A (en) | Method for preparing dihydric alcohol ester by using reactive distillation process | |
| CN1224454C (en) | Catalyst for direct synthesis of methyl carbonate and its prepn | |
| CN1043313C (en) | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof | |
| CN1086508A (en) | The method for making of formic acid | |
| CN111393397B (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN1120049C (en) | Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate | |
| CN1394678A (en) | Catalyst for synthesizing dimethyl carbonate and its preparation method | |
| CN1915938A (en) | Method for producing ethene and hexene through dismutation of butylene | |
| CN1248237A (en) | Process for manufacture of carboxylic acids | |
| CN1519052A (en) | A load of Pd hydrogenation catalyst and preparation method as well as method for preparing cyclohexanone from phenol by using the catalyst | |
| CN113461652B (en) | Method for preparing epsilon-caprolactone by catalytically oxidizing cyclohexanone in presence of molecular oxygen | |
| CN1076218C (en) | One step method for synthesis of catalyst for 2, 5 -dimethyl-2, 4 -hexadiene reaction and its application | |
| CN1095396C (en) | Catalyst carrying inorganic potassium compound | |
| CN1047106C (en) | Zeolite catalyst for producing p-methyl-ethyl benzene with ethylene and toluene | |
| CN1089276C (en) | Carried hydrotalcite catlyst and the preparation of aliphatic alcohol ether acetate | |
| CN1228297C (en) | Method for synthesizing dialkoxy propane | |
| CN113509956B (en) | Molecular sieve catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |