CN85105846B - Method for making compound of pyrazine - Google Patents
Method for making compound of pyrazine Download PDFInfo
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- CN85105846B CN85105846B CN85105846A CN85105846A CN85105846B CN 85105846 B CN85105846 B CN 85105846B CN 85105846 A CN85105846 A CN 85105846A CN 85105846 A CN85105846 A CN 85105846A CN 85105846 B CN85105846 B CN 85105846B
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- catalyst
- pyrazine
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Abstract
The present invention relates to a method for making pyrazine compounds. Glycol and diamine compounds are used as raw materials which are catalyzed and synthesized into pyrazine compounds through gas phase under the action of catalysts. Due to the adoption of the novel synthetic pyrazine catalysts after one or a plurality of other metal elements, such as magnesium, cerium, aluminium, manganese, cuprum, ferrum, calcium, silicon, chromium, etc. are added to zinc oxide, the yield of products is increased by more than 10 %, and the optimal operating temperature is reduced by about 100 DEG C. The cost of the products is reduced, and energy consumption is lowered.
Description
The present invention is about being raw material with glycols and diamine compounds, in the presence of catalyst, carries out gas phase catalytic reaction, makes the method for pyrazine compounds.
Pyrazine compounds is a kind of food flavor, also is synthetic medicine, the intermediate that agricultural chemicals etc. are important.In the past, mainly be that the method with the piperazine compounds gas-phase dehydrogenation prepares (seeing United States Patent (USP) No. 2400398), yet because this method raw material valency is expensive, not too economical.In recent years, having with glycols and diamine compounds is raw material, with zinc oxide be main body as catalyst, the method for the synthetic pyrazine compounds of gas phase catalysis (seeing special permission communique 55-50024), but because of yield lower (64～70%).Operating temperature height (optimum operating temperature 450-500 ℃), energy consumption is big, so uneconomical.
The objective of the invention is to solve existing problem in the synthetic pyrazine compounds method of existing gas phase catalysis.
The present invention has developed novel pyrazine compounds synthetic catalyst, has set up corresponding gas phase catalysis synthetic method.Be that raw material two pure and mild diamine compounds directly mix, or its mixture is dissolved in a kind of appropriate solvent by gasification back and rare pneumatosis sends in the lump in the reaction tube that catalyst of the present invention is housed, carry out gas phase catalytic reaction at a certain temperature.Product reclaims after cooling off.Novel pyrazine compounds synthetic catalyst is based on zinc oxide, adds wherein one or more metallic elements of aluminium, copper, silicon, calcium, and the latter can be that oxide, salt or metallic state exist.Also can obtain higher yield with zinc oxide separately, but when adding above-mentioned element, yield is higher.The content of one or more metals in catalyst such as aluminium, copper, silicon, calcium do not have special restriction, generally 0.1～25% more suitable, are preferably in 1～15%.This catalyst can be with kneading method or immersion process for preparing.As: make Zinc oxide catalytic in advance, the aequum metal impregnation is got on again, or it is sneaked in the zinc oxide with kneading method, dry again, roasting forms.The raw material glycols general formula that the present invention uses is
, the diamine compounds general formula is
(R in the formula
1～R
8Be hydrogen atom or alkyl).Glycols can be an ethylene glycol, 1, and the 2-propane diols, 2, the 3-butanediol, 1, the 2-butanediol, 1, the 2-cyclohexanediol, 1, the 2-pentanediol, 2, the 3-pentanediol, 1,2-encircles pentanediol, benzoglycols, 3,4-hexylene glycol etc.Two amines: can be ethylenediamine, 1,2-butanediamine, 2,3-butanediamine, 1,2-cyclohexanediamine etc.Raw material difference, the pyrazine compounds that obtains are also different.During as usefulness ethylenediamine and ethylene glycol, make pyrazine,, when 2-propane diols and ethylenediamine, make the 2-methylpyrazine with 1; With 2,3-butanediol and 1 during the 2-propane diamine, makes 2,3,5-trimethylpyrazine etc.The inert gas of solvent that uses among the present invention and dilution usefulness must be stable under reaction condition.As: what can be used as solvent has benzene or toluene or water, or cyclohexane etc.What can be used as carrier gas has nitrogen or ammonia, or argon or hydrogen, or lower hydrocarbon etc.The ratio of raw material glycol or diamines, no matter any some more can, but because when excessive, accessory substance is more, preferably waits the gram molecule mixing.Add the amount of solvent, be 40～60% of material liquid.The suitable reaction temperature of catalyst is 320～500 ℃, and optimum temperature is 340～400 ℃.During reaction, the air speed of raw material mixed liquor is different and different with the granularity of using catalyst, and can change in the scope of broad: when catalyst grain size was 10～20 orders, liquid air speed was 0.5～3.0hr
-1, 1～2.5hr preferably
-1Change air speed, also can use φ 4 * 5～10mm original catalyst particle size.
Advantage of the present invention is: owing to adopted new catalyst in the synthetic method, make the yield of pyrazine compounds improve more than 10%, optimum operating temperature has reduced about 100 ℃, and product cost reduces, and energy consumption reduces.
Example
1. make with infusion process or kneading method, based on zinc oxide, the catalyst 60ml that adds metals such as small amount of aluminum, copper, calcium, silicon, granularity 10～20 orders, the internal diameter of packing into is in the φ 25mm stainless steel reactor, the catalyst layer temperature remains on 360～380 ℃, 1,2-propane diols and ethylenediamine etc. the gram molecular solution dilute with water make 40%(V/V) the aqueous solution, with the speed gasification back feeding catalyst layer of this material liquid with 1.3ml/min, react after 30 minutes product is cooled off, reclaim, analyze with gas-chromatography.Solution contains 2-methylpyrazine 24.7%, and 2-methylpyrazine yield is 79.4.
2. with 2,3-butanediol and ethylenediamine are raw material, and both ratios and amount of water prepare 2 with example 1 with example 1 identical device and condition, and the 3-dimethyl pyrazine reacts and collects reactant liquor after 30 minutes, analyzes with gas-chromatography.Solution contains 2, and 3-dimethyl pyrazine 26.1%, 2, the yield of 3-dimethyl pyrazine are 81.3%.
Claims (6)
- It is 1, a kind of that (general formula is with two amines and glycols compound
-
- R in the formula 1～R 6Be hydrogen atom or alkyl) be raw material, by catalyst based on zinc oxide, the method of the synthetic pyrazine compounds of gas phase catalysis, it is characterized in that having added one or more metallic elements such as copper, calcium, silicon in the main body catalyst oxidation zinc, its content is generally 0.1～25%, and operating temperature is 320～500 ℃.The ratio of two pure and mild diamines classes in the material liquid, no matter any some morely all can.The ratio of solvent is 40～60%.During reaction, when being 10～20 orders as if catalyst grain size, the material liquid air speed then is 0.5～3.0hr -1, change air speed, also available φ 4 * 5～10mm original catalyst particle size.
- 2, by the described manufacture method of claim 1, the content that it is characterized in that copper in the catalyst, calcium, silicon etc. preferably 1～15%.
- 3, by the described manufacture method of claim 1, it is characterized in that optimum operating temperature is 340-400 ℃.
- 4,, it is characterized in that the ratio of two pure and mild diamines preferably waits gram molecule to mix by the described manufacture method of claim 1.The material liquid air speed is preferably 1～2.5hr -1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105846A CN85105846B (en) | 1985-07-31 | 1985-07-31 | Method for making compound of pyrazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105846A CN85105846B (en) | 1985-07-31 | 1985-07-31 | Method for making compound of pyrazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105846A CN85105846A (en) | 1986-07-09 |
| CN85105846B true CN85105846B (en) | 1988-02-17 |
Family
ID=4794746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105846A Expired CN85105846B (en) | 1985-07-31 | 1985-07-31 | Method for making compound of pyrazine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85105846B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948763A (en) * | 1995-08-04 | 1997-02-18 | Koei Chem Co Ltd | Production of pyrazine |
| CN103949266B (en) * | 2014-05-15 | 2016-03-30 | 西安元创化工科技股份有限公司 | Take isopropanolamine as catalyst and the preparation method of Material synthesis 2,5-dimethyl pyrazine |
| CN108484512B (en) * | 2018-05-23 | 2020-05-05 | 滕州市悟通香料有限责任公司 | Method for synthesizing 2,3, 5-trimethylpyrazine |
-
1985
- 1985-07-31 CN CN85105846A patent/CN85105846B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105846A (en) | 1986-07-09 |
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