CN1091001C - Catalyst for preparation of metaphenylene dimethylamine - Google Patents
Catalyst for preparation of metaphenylene dimethylamine Download PDFInfo
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- CN1091001C CN1091001C CN99113994A CN99113994A CN1091001C CN 1091001 C CN1091001 C CN 1091001C CN 99113994 A CN99113994 A CN 99113994A CN 99113994 A CN99113994 A CN 99113994A CN 1091001 C CN1091001 C CN 1091001C
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- xylene diamine
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Abstract
The present invention relates to a catalyst for preparing metaphenylene dimethylamine, which mainly solves the defects of high production cost and small catalyst load in the existing literatures. The present invention adopts a technical scheme that cobalt, titanium and platinum are loaded on silicon dioxide or kieselguhr, and molybdenum, barium, stannum, magnesium, calcium, chromium, strontium or tungsten is selected and added without coerciveness, so that the defects are well solved. Therefore, the present invention can be used in industrial production.
Description
The present invention relates to a kind of catalyst that is used to prepare m-xylene diamine.
M-xylene diamine (English name m-xylylenediamine or α, α-diamine-m-xylene, molecular formula C
8H
12N
2, 14 ℃ of fusing points, 248 ℃ of boiling points) and be a kind of colourless, have the liquid of almond flavor.M-xylene diamine is a kind of important Organic Ingredients intermediate, is mainly used in the manufacturing epoxy curing agent, photo-plastics, rubber chemicals, and polyurethane resin and coating etc.In addition, also can be used for aspects such as agricultural chemicals, fibre finish agent, antirust agent, chelating agent, lubricant, paper conversion agent.From the synthetic m-xylene diamine of isophthalodinitrile catalytic hydrogenation, existing lot of documents report.Because reasons such as pressure height (greater than 20.0MPa), feed stock conversion is low, catalyst life is short still exist many problems so far.Introduced a kind of method of reducing of aromatic nitriles among the clear 56-63944 of document.When being raw material with the isophthalodinitrile in the document, under the carbon dioxide coexistence, with 5% (weight) palladium/Al
2O
3Being catalyst, is under 60～78 ℃ of conditions in reaction temperature, hydrogenating reduction 60 minutes, and the yield that obtains the product m-xylene diamine is 86.6%, its catalyst/isophthalodinitrile (weight ratio) is 10%.Introduced a kind of technology of producing catalyst in the document US 4343722.It is to be catalyst with the cobalt octacarbonyl, and its catalyst/isophthalodinitrile (weight ratio) is 7.6～12.5%, and reaction temperature is about 160 ℃, and reaction pressure is up to 26.0MPa.It is solvent with the meta-xylene, and liquefied ammonia is inhibitor, m-xylene diamine yield about 94～96%.Do not relate to the life of catalyst problem in addition in the document.Introduced a kind of preparation method of dimethylphenylene diamine in the document US 4482741.Titanium with the cobalt and 4% (weight) of 60% (weight) in the document is carried on the solid carrier as catalyst.With the m-xylene diamine is solvent, reaction is 8 hours under reaction pressure 7.5MPa condition, wherein catalyst/isophthalodinitrile weight ratio is 11.7%, use for the first time, the yield of its m-xylene diamine is 88%, when circulation was used for the second time, the yield of its m-xylene diamine was 94%, had only reported the situation of catalyst circulation use secondary in addition in the document.
The objective of the invention is to contain cobalt amount height in the conventional art in the catalyst in order to overcome, cause catalyst cost height, and catalyst loading is little, and promptly the little shortcoming of the output of unit catalyst in the unit interval provides a kind of catalyst that is used to prepare m-xylene diamine.It is low that this catalyst has a production cost, the characteristics that catalyst loading is big.
The objective of the invention is to realize by following technical scheme: a kind of catalyst that is used to prepare m-xylene diamine is a carrier with silica gel or diatomite, the following active constituent of load on carrier, and the percentage that accounts for vehicle weight is:
A) 5～30% cobalt;
B) 0.1～10% titanium;
C) 0.005～0.5% palladium;
D) 0～2% at least a molybdenum, barium, tin, magnesium, calcium, chromium, strontium, tungsten or the plumbous element of being selected from.
The percentage preferable range that the cobalt of load accounts for vehicle weight on carrier in the technique scheme is 10～30%; The percentage preferable range that the titanium of load accounts for vehicle weight is 0.5～5%; The percentage preferable range that the palladium of load accounts for vehicle weight is 0.01～0.3%; The percentage preferable range that at least a element that is selected from molybdenum, barium, tin, magnesium, calcium, chromium, strontium or tungsten of load accounts for vehicle weight is 0.01～0.8%.
In the technique scheme, cobalt, titanium use simultaneously, help to reduce the pressure of reaction; In catalyst, introduce palladium, help further improving activity of such catalysts, reduce the consumption of cobalt; Introducing is selected from the yield that molybdenum, barium, tin, magnesium, calcium, chromium, strontium, tungsten or plumbous element help further improving purpose product m-xylene diamine.
Method for preparing catalyst of the present invention is as follows:
At first with institute's expense palladium bichloride, titanium chloride, cobalt chloride and non-imposed adding be selected from barium, tin, magnesium, calcium, chromium, strontium, tungsten or plumbous chloride and molybdate wiring solution-forming after be impregnated on silica gel or the diatomite, then with the reducing agent that is selected from formaldehyde, hydrazine hydrate or boron hydrohalogenic acid salt, under normal pressure, reduce, after washing, drying, get catalyst.
The present invention has improved activity of such catalysts owing to introduce palladium in cobalt, titanium catalyst system and catalyzing, makes catalyst under the situation of low cobalt content, still can keep the yield of m-xylene diamine.Because cobalt element costs an arm and a leg, therefore can reduce production costs greatly.Simultaneously because cobalt, titanium and palladium system have very high activity and selectivity of product, and after adding the element that is selected from molybdenum, barium, tin, magnesium, calcium, chromium, strontium, tungsten or lead, then make the catalytic performance of catalyst obtain further strengthening, the output of the unit's of making catalyst in the unit interval increases greatly, the big characteristics of catalyst loading have been embodied, its catalyst/isophthalodinitrile (weight ratio) can reduce to 5%, also can reach 95.3% and the yield of m-xylene diamine is the highest, this moment, cobalt content had only 30% (weight), had obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
With isophthalodinitrile 30 grams, 30 milliliters of methylamines, 70 milliliters of dimethylbenzene join in 300 milliliters the autoclave, and (accounting for vehicle weight percentage is 20% cobalt to add 1.5 gram catalyst then, 2% titanium and 0.01% palladium/diatomite), use nitrogen replacement, and logical hydrogen stirs (rotating speed is 500 rev/mins) and is heated to 130 ℃ to being 5.0MPa in the gauge pressure reaction pressure, this moment, system pressure was counted 6.0MPa with gauge pressure, constantly feed hydrogen, do not have obvious absorption, reacted about 5 hours until hydrogen.Leave standstill and be cooled to room temperature, topple over and the upper strata reactant liquor.Reactant liquor distills under normal pressure and reclaims methylamine and dimethylbenzene, the decompression distillation m-xylene diamine, and being collected in gauge pressure is 6665Pa, 130～135 ℃ of fractions, get m-xylene diamine 28.9 grams, catalyst/isophthalodinitrile weight ratio is 5%, and the m-xylene diamine yield is 90.8%.[embodiment 2]
Each Step By Condition according to embodiment 1, just changing catalyst consists of: to account for the vehicle weight ratio be 25% cobalt, 1.5% titanium, 0.1% palladium and 0.01% molybdenum/diatomite to the active constituent of load on the diatomite, get m-xylene diamine 29.7 grams, the m-xylene diamine yield is 93.2%.[embodiment 3]
Each Step By Condition according to embodiment 1, just changing catalyst consists of: to account for the vehicle weight ratio be 5% cobalt, 10% titanium, 0.5% palladium, 1.2% barium and 0.8% molybdenum/diatomite to the active constituent of load on the diatomite, get m-xylene diamine 27.9 grams, the m-xylene diamine yield is 87.5%.[embodiment 4]
Each Step By Condition according to embodiment 1, just changing catalyst consists of: to account for the vehicle weight ratio be 30% cobalt, 2% titanium, 0.3% palladium, 0.2% chromium and 0.6% barium/diatomite to the active constituent of load on the diatomite, get m-xylene diamine 30.4 grams, the m-xylene diamine yield is 95.3%.[embodiment 5]
Each Step By Condition according to embodiment 1, just changing catalyst consists of: to account for the vehicle weight ratio be 10% cobalt, 6% titanium, 0.3% palladium and 0.1% tin/diatomite to the active constituent of load on the diatomite, get m-xylene diamine 29.4 grams, the m-xylene diamine yield is 92.1%.[embodiment 6]
Each Step By Condition according to embodiment 1, just changing catalyst consists of: to account for the vehicle weight ratio be 15% cobalt, 3% titanium, 0.1% palladium and 0.2% plumbous and 0.5% chromium/diatomite to the active constituent of load on the diatomite, get m-xylene diamine 28.3 grams, the m-xylene diamine yield is 94.3%.[comparative example 1]
According to each Step By Condition of embodiment 1, just change catalyst and consist of: to account for the vehicle weight ratio be 20% cobalt and 4% titanium/diatomite to the active constituent of load on the diatomite, m-xylene diamine 24.1 grams, the m-xylene diamine yield is 75.6%.
Claims (5)
1, a kind of catalyst that is used to prepare m-xylene diamine is a carrier with silica gel or diatomite, the following active constituent of load on carrier, and the percentage that accounts for vehicle weight is:
A) 5～30% cobalt;
B) 0.1～10% titanium;
C) 0.005～0.5% palladium;
D) 0～2% at least a molybdenum, barium, tin, magnesium, calcium, chromium, strontium, tungsten or the plumbous element of being selected from.
2,, it is characterized in that the percentage that on the carrier cobalt of load accounts for vehicle weight is 10～30% according to the described catalyst that is used to prepare m-xylene diamine of claim 1.
3,, it is characterized in that the percentage that on the carrier titanium of load accounts for vehicle weight is 0.5～5% according to the described catalyst that is used to prepare m-xylene diamine of claim 1.
4,, it is characterized in that the percentage that on the carrier palladium of load accounts for vehicle weight is 0.01～0.3% according to the described catalyst that is used to prepare m-xylene diamine of claim 1.
5,, it is characterized in that the percentage that on the carrier at least a element that is selected from molybdenum, barium, tin, magnesium, calcium, chromium, strontium or tungsten of load accounts for vehicle weight is 0.01～0.8% according to the described catalyst that is used to prepare m-xylene diamine of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113994A CN1091001C (en) | 1999-08-19 | 1999-08-19 | Catalyst for preparation of metaphenylene dimethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113994A CN1091001C (en) | 1999-08-19 | 1999-08-19 | Catalyst for preparation of metaphenylene dimethylamine |
Publications (2)
| Publication Number | Publication Date |
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| CN1285236A CN1285236A (en) | 2001-02-28 |
| CN1091001C true CN1091001C (en) | 2002-09-18 |
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|---|---|---|---|
| CN99113994A Expired - Fee Related CN1091001C (en) | 1999-08-19 | 1999-08-19 | Catalyst for preparation of metaphenylene dimethylamine |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1663947B1 (en) | 2003-09-10 | 2008-01-16 | Basf Aktiengesellschaft | Method for the production of diaminoxylene by continuous hydrogenation of liquid phthalonitrile |
| WO2007014901A1 (en) | 2005-08-02 | 2007-02-08 | Basf Se | Process for preparing xylylenediamine by continuous hydrogenation of phthalonitrile |
| CN101214444B (en) * | 2007-01-04 | 2010-04-21 | 北京有色金属研究总院 | Catalyst for sodium borohydride catalyzing hydrolyzation hydrogen supplying method and preparation thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247478A (en) * | 1979-11-16 | 1981-01-27 | Suntech, Inc. | Process and catalyst for hydrogenation of aromatic dinitriles |
| US4482741A (en) * | 1984-01-09 | 1984-11-13 | Uop Inc. | Preparation of xylylenediamine |
| JPH0940630A (en) * | 1995-08-02 | 1997-02-10 | Showa Denko Kk | Production of aromatic cyanomethylamine |
-
1999
- 1999-08-19 CN CN99113994A patent/CN1091001C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247478A (en) * | 1979-11-16 | 1981-01-27 | Suntech, Inc. | Process and catalyst for hydrogenation of aromatic dinitriles |
| US4482741A (en) * | 1984-01-09 | 1984-11-13 | Uop Inc. | Preparation of xylylenediamine |
| JPH0940630A (en) * | 1995-08-02 | 1997-02-10 | Showa Denko Kk | Production of aromatic cyanomethylamine |
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