Process for producing nitriles of fatty acids or their mixtures

专利摘要:

公开号:SU971092A3
申请号:SU782650552
申请日:1978-08-18
公开日:1982-10-30
发明作者:Билленштайн Зигфрид；Кукла Бруно；Штюлер Херберт
申请人:Хехст Аг(Фирма)；
IPC主号:

专利说明:

(54) METHOD FOR OBTAINING NITRILES OF FATTY ACIDS OR THEIR MIXTURES
I
The invention relates to methods for producing nitriles of fatty acids or their mixtures and gritsirina, which are widely used as intermediates in organic synthesis .5
There is a known method for the preparation of nitriles and glycerol from glycerides in two stages, namely, first glycerides are subjected to saponification, during which glycerol and fatty acids are separated, and then fatty acids. Acids are treated with 10 ammonia.
The disadvantage of this method is its two-stage process.
There is also known a method of producing nitriles of fatty acids in the hard phase by treating glycerides with gaseous ammonia mixed with nitrogen (20 l / h), which is passed through at a rate of 500 l / h at 0.75–1 kg of glyceride per hour at 350- 400 ° C in the presence of bauxite as a catalyst, followed by the separation of 20 volatile products withdrawn into phases — organic and aqueous. If necessary, the nitrile is cleaned with water and washed with hydrochloric acid and soda solutions. The output of the crude nitriles 98-100% 1. y
The known method does not allow, under the 1x conditions, to prepare from glycerides simultaneously with. nitriles and glycerin, since the latter is almost completely decomposed during the reaction. In addition, decomposition products contaminate the target nitriles and with great difficulty are separated from them, which makes it difficult or impossible to use nitriles for the intended purpose.
The purpose of the invention is the simultaneous production of nitriles of fatty acids or their mixtures and glycerin, as well as simplification of the process.
The goal is achieved according to the method of obtaining nitriles of fatty acids of the general formula
Ri (R2R3) CN or RjCN,
where RI, Rj. Ra - alkyl radicals with h with a scrap of carbon atoms 3-23i
or mixtures thereof by treating glycerides I of the general formula
szng-OH dH - OY. dHz -odoRi where X is CORj or H; Y - СОВз or Н; RI, RJ. RS have the indicated values, or their mixtures in the cold phase with gaseous ammonia supplied at a rate of 500-690 l / kg glyceride per hour at 220-300 ° C. in the presence of a catalyst, 1–4% by weight of the glyceride of lead salts, or cadmium, or neja, or cobalt, or zinc mono- or dicarboxylic, saturated or unsaturated aliphatic acid with 4–24 carbon atoms, benzene-, or naphthalene mono- or dicarboxylic acid, substituted by akyl radical with 1-12 carbon atoms, alkane mono or alkane disulfonic acid, benzene or naphthalene mono- or disulfonic acid substituted with an alkyl radical with 1-12 carbon atoms, or a mixture of these, followed by separation of the volatile mixture of products removed from the reaction zone to phases - fatty acid nitrile and glycerin-water - and release from them. target products. The process is carried out at 220-240 ° C before removal of glycerol from the reaction zone in an amount of 130-68% by weight of the reaction mass, followed by heating the reaction mixture directly or stepwise for 0.5-5 hours to 270-300 ° C. The nitrile phase is subjected to subsequent treatment with ammonia supplied at a rate of 150 l / kg-h of nitrile at 220-300 ° C in the presence of these catalysts. The yield of the target nitriles 93-98%. Content is free; fatty acids not more than 2% and their amides 6-15%. The yield of crude glycerol (after separation of water by dissipation) is up to 96%. After additional treatment of the nitrile phase with ammonia, the fatty acids in the target nitriles are 0.1–1.5 wt.%, And their amides are 0.1–2. . Thus, the proposed method provides simultaneous production of nitriles of fatty acids in one stage directly from glycerides with a sufficiently high yield, and with a sufficient degree of purity with respect to the content of free fatty acids and their ashad. In addition, the process is not accompanied by the decomposition of glycerol, and the target reagents are not contaminated by the difficult products of its decomposition. EXAMPLE 1. The reaction is carried out in a heated reactor with a capacity of 800 cm, equipped with a gas injection device, an agitator, installed inside a thermome: thunder and a fractional column, which is a steel tpy6y with a length of 20 cm and a diameter of 1, 5 cm, filled with Raschig rings and a collection system consisting of three series-connected collections in which the volatile reaction products condense. This system is loaded with 495 g of lamb fat (cornmeal ratio 190, acid number 7, 6), and also 5 g of db dehalbenzenesulfonate zinc as a catalyst. During the reaction, the apparatus is flushed with nitrogen. Then, instead of nitrogen, ammonia is supplied to the system at the rate of 600 liters of ammonia per 1 kg of fat per hour. Fresh ammonia is continuously supplied during the reaction. The temperature in the reactor is maintained in the reactor. 1. After 7 hours, the reaction of the reaction of fat with ammonia is completed. The polluted fatty acid nitrile and glycerin are captured by two successively included collectors. In the last collection collect condensed ammonia reaction water. The glycerin and lamb nitrile collected in the two first collections during the reaction are divided into two phases, after which the lamb fat is washed with water. The yield of lamb nitrile thus produced is 93.6% (413.7 g) of theory. The amide content of 1.8 wt.%, The fatty acid content of fat 1.5 wt.%. The content after processing of pure glycerol 80.2% (39.6 g). (Here and hereinafter, the yield is indicated as a percentage of the theoretical). Example 2. In the apparatus described in Example 1, 495 g of beef glanders (190 coefficient, acid number, 1.6) and 10 g of zinc dodecylbenzenesulfonate are introduced. Starting with 230 ° C, ammonia is passed through the fat at a rate of 600 liters per 1 kg of fat per 1 hour. The temperature in the reactor is maintained as follows: Reaction time. Temperature in the reactor, ° C 30230 20 235 20240 20245 70250 80255 30260 60270 60280 60290 Common the reaction time is 7.5 hours. The products entering the collections are washed with water and additionally processed. The output of fatty acid nitrile is 92.3% (408 g). At a content of 0.7% by weight of acude and 0.5% by weight of fatty acid. The yield of crude glycerol is 87.7% (44.7 g). Separate crude glycerin (OH number 1694) contains 81.2% glycerol (relative to the used fat). Example 3. In the apparatus described in Example 1, 445 grams of technical fat (bleached) with a saponification ratio of 186 and an acid number of 12.6, and also 9 grams of zinc dodecylbenzenesulfonate are introduced. The reaction is carried out under the conditions described in Example 2 using ammonia. Introduced during the reaction for 7.5 hours, the products were combined and the glycerin was washed out with water. The yield of fatty acid nitrile is after the separation of the aqueous phase of 93.0% (370.4 g), with an amide content of 0.5% by weight, and of idric acids 0.3% by weight. From the aqueous phase, 97.5% glycerol (38.5 g) is obtained - yield 97.5%. The yield of pure glycerol (OH number 1683) is 84.0% relative to the fat used. Example 4. In the apparatus described in example 1, in which in this case a fractional column 70 cm long made of mirror glass, filled with a ring, Raschig is used, 488 grams of edible fat is loaded (coefficient of saponification 190, acid number 2.4) and 5 g zinc toluene sulfoate. During heating, ammonia is passed through the reactor at the rate of 600 l per 1 kg of fat in Ih. The reaction is continued for 3 hours at 230 ° C. Then, within half an hour, the temperature is raised to 270 ° C and maintained for 3.25 hours. After 3 hours 42% glycerol is derived. After 6.75 hours, all volatile products are removed from the reactor from the top of the column. The mixture of glycerin-nitrile fat collected in the collection system is further treated with water. After treatment of both phases, nitrile is obtained, the yield of which is 93.2% (406 g) with an amide content of 0.5% by weight, a fatty acid of 0.5% by weight. The yield of pure glycerol is 80.1% (40.1 g). In the same apparatus and under the same conditions, the processing of food glue in the presence of other catalysts is carried out. The results are shown in tab. 2 Example 5. The apparatus described in Example 4 was injected with 436 g of sunflower oil (saponification factor 189, acid number 0.8) and 9 g of zinc dodecylbenzenesulfonate used as a catalyst. Conditions similar to example 4 are established (reaction time is 6.75 hours, ammonia is 690 liters per 1 kg of oil per 1 hour. After 3 hours, the amount of glycerol removed is 37% of the theoretical value. As a result of processing, 94.6% of oil nitrile is obtained with amide 0.5 wt.%, fatty acid 0.35 wt.%. The yield of crude glycerol is 91.2% (40.9 g), and the yield of pure glycerin (NUM IT 1717) is 85.6% (relative to the injected oil EXAMPLE 6: The preparation of a fatty acid nitrile and glycerin is carried out from a glyceride in an uninterrupted manner, B heated by hearth A 750 ml food vessel with 19 ml of food grade salt and 7.5 g of zinc dodecylbenzene sulphonate is added to the reactor.The reactor is equipped with a stirrer, an internal thermometer, a heated funnel with a dropper and a 70 cm column filled with Raschig rings. 600 liters per kg of fat per hour. In these conditions, 1009 liters of edible fat mixed with 1% by weight of zinc dodecylbazole sulfonate are introduced into the reactor for 36 hours (27–29 grams of fat in 1 hour). Continuously volatile products leaving the reactor are condensed in the collection system. Nitrile fat clear of glycerol with water. The yield of fat nitrile is 96.1% (1033 g), the amount of amides is 1.4% by weight. 115.4 g of crude glycerin (95.5% yield) is taken from the water. EXAMPLE 7 The apparatus described in example 4 was filled with 486 g of edible fat (emissivity 190, acid number 1.6) and 5 g of dodecylbenzenesulfonate sugar. At 270 ° C, ammonia is continuously passed through the reaction mixture at a rate of 500 l per 1 kg of fat per 1 hour. The reaction time is 6.5 hours. The reaction products received by the collections are washed with soda and processed. 406 g (93.7%) of fat nitrile are obtained with an amide content of 2.2% by weight and a fatty acid of 0.4% by weight. 36.8 g (73.45%) of pure glycerin is obtained in relation to this fat. Example 8. In the apparatus described in Example 4, 486 g of mutton fat (saponification ratio 187.5, acid number 11.1) and 4.25 g of the zinc salt of fat acid were introduced. In the process of heating, ammonia is passed through the reactor at the rate of 600 l per 1 kg of fat per hour. After 13 hours the reaction is completed. The amount of glycerin added after 3 hours at 230 ° is 32% of the theoretical. At the same time, the reaction temperature is maintained for 9.5 hours at the level of 270 ° C. The products of the processing of fat accumulated from the reactor are accumulated in the collections and washed with water. The yield of nitrile fat was 367.8 g (84.6%). 28.3 g (60.4%) of pure glycerol was obtained with respect to the fat. Example 9. In the apparatus described in example 1, equipped with the fractional column specified in example 4, 445 g of beef sap (coefficient of yummy 186, acid number 0.8) and 9 g of dodecylbenzene sulfate ferric iron used as a catalyst are introduced. First, at 230 ° C, ammonia is passed through the fat j at the rate of 6СУ l per 1 kg of fat per hour. For 7.25 hours the temperature is raised to 290 ° C. At the end of the reaction and processing, 364.1 g of fat nitrile are obtained (yield 91, 4%), Amide content of 2.9 wt.%, Gift of acid, 0.4 wt.%. The yield of pure glycerol was 30.2 g (67.0%) based on salted fat.
PRI me R 10. The apparatus described in the example was loaded with 445 g of beef tallow (saphenium ratio 190, acid number 0.2) and 9 g of lead dodecylbenzenesulfonate. Starting with a reaction temperature of 230 ° C, ammonia is passed through reactor I at a rate of 600 liters per kg of fat per hour. The reaction temperature is raised in 7.25 hours to 290 ° C. At the end of the reaction and processing, 350.5 g of nitrile are obtained (yield 88, 2%) with an amide content of 2.7% by weight and a fatty acid of 0.35% by weight. 36.5 g of pure glycers are obtained (yield 78.9%) .-
Example. In the apparatus described in the example, 445 g of soybean oil (saponification factor 203.2) and 9 g of zinc dodeylbenzenesulfonate are loaded. Starting from 230 ° C ammonia is passed through the oil at the rate of 600 l per kg of oil per hour. For 7.25 hours, the reaction temperature is increased to 290 ° C. At the end of the reaction and processing, I get 363.3 g of soy nitrile (yield 92.2) when the content of the amide is 0.7 wt.%, h fatty acid 0.7 wt.%. Pure glycerol get 36.0 g (yield 72.8%) in relation to the amount of used oil.
Example 2. The apparatus described in Example 1 is loaded with 445 g of beef tallow (saponification factor 92, acid number 0.25) and 9 g of dodecylbenzenesulfonate. cadmium. Starting with 230 ° C, 600 l of ammonia Hia kg of fat per hour are passed through the mass. For 6.5 hours the temperature of the reaction mixture is raised to 290 ° C. At the end of the reaction and processing, 373.6 g of fat nitrile are obtained (up 94.2%) with the content of amides of 2 wt.% and fatty acid 0.7 wt.%. The yield of pure glycerol is 35.1 g (75.2%).
Example 13: 445 g of beef tallow (saponification ratio 192) and 9 g of cobalt dodecylbenzenesulfonate are loaded into the apparatus described in Example 1. Starting with 230 ° C, 600 l of ammonia are passed through the mass. aka per 1 kg of fat in 1 hour. For 7.25 hours, the temperature is raised to 290 ° C. At the end of the reactions and processing, the yield of nitrile of fat is 94% (373 g) with an amide content of 4.9% by weight, fatty acid 0 , 8 wt.%. The crude glycerin yield is 86.4% J40J). I Example 4: In the apparatus described in example 1, 486 g of edible fat (coefficient of oatmeal is 187, acid number 0.8) and wt.% Zinc dodecylbenzenesulfonate (calculated as fat) are loaded. In the conversion process, ammonia is passed through the reactor at the rate of 600 liters of ammonia per kg of fat per hour. The temperature is maintained at 230 ° C for 3.0 hours. The amount of glycerol removed is 64% of the theoretical value, then after half an hour heating the temperature is kept in within 1.25 hours at a level of 270 ° C. Reakvdu is completed after 4.75 hours. The reaction products (collected at collections of 230 ° C and 270 ° C) are collected separately and processed. Nitrile fat, etched at 230 ° C, contains 20 wt.% Amide. At 270 ° C, the amide content is 9% by weight. The total amide content in nitrile fatty acid is 10%.
Example 15. In the apparatus described in the example, the round in which, however, the fractional column is replaced with a direct adapter from the reactor to the collection system, 500 g of sheep's fat (coefficient of cleansing 189, acid number 0.9) and 2% (by weight of sheep's fat) zinc-dodecylbenzene sulfonate. During the reaction, ammonia is passed at a rate of 600 liters per 1 kg of fat per hour. The temperature is maintained at 230 ° C for 3 hours. The amount of glycerol extracted is 67% of theoretical. During each subsequent hour, the temperature was increased by 10 ° C. The reaction was completed at 280 ° C. The total reaction time was 5.25 hours. The whole condensate was separated by water at 80 ° C to fatty acid nitrile and glycerin-water. Isolated pitril fatty acid contains 5.3 wt.% Amide and 0.5 wt.% Fatty acid. The yield of nitriles is 95.2%. After processing, 91.4% pure glycerol is obtained.
Example 16. A heated reactor equipped with a gas inlet pipe, an agitator with an internal thermometer and a connected collection system (condensation system consisting of one or a series of collections, tanks) is loaded. 500 g of technical fat (emissivity 191.4, acid number 1.5) and 2 wt.% (Relative to fat} zinc-dodecylbenzenesulfonate. After heating to 230 ° C, ammonia is passed through the reaction mass at a rate of 600 l per 1 kg of fat in 1 h. The amount of extracted glycerol is 68% of the theoretical one. After 3 hours, the temperature is continuously set at 1.5 hours to 250 ° C. After 4.5 hours, the glycerin is gone, about half of the fatty nitrile is removed from the reactor; jjibix acids. From this point on, the transmission of ammonia through the reaction mass decreases to 60 liters per kg of fat per hour, and the reaction temperature is simultaneously increased to 290 ° C. During the preheating process, water-containing glycerin is washed with crude nitrile, which is then returned to the reactor after the glycerin has been washed. A total of 6.5 hours (additional reaction lasts 2 hours), the nitrile is isolated and purified by catalyst distillation. I get 417 g (93.2% yield) of a fatty acid nitrile containing less than 0.05 wt.% amide , with an acid number of 0.1. The amount of glycerol (by the number of OH) is 42.9 g (yield 82.7%). Example 17. The apparatus described in Example 16 is loaded with 500 g of lower grade technical animal fat (saponification factor 191.4, acid number 1.5) and 2 wt.% Zinc dodecylbenzenesulfonate (calculated as animal fat). During STVI interactions, I ammonia is passed through the reaction mixture at the rate of 600 l per 1 kg of fat per: 1 h, and the temperature for 3 hours is equal to 230 ° C and then continuously along,. within 2.25 hours to 280 ° C. The total reaction time is 5.25 hours. During the conversion, the temperature difference between the bottom and the distillate is as small as possible: m. The resulting condensate is separated by with water to crude fatty acid nitriles and glycerin. 432.8 g (96.7% of the calculated) crude fatty acid nitriles with an amide content of 6.1 wt.% And fatty acids of 0.7 wt.% Were added. The yield of crude glycerol is 49.4 g (95% based on the calculated yield), from which I can obtain 47.3 g (91.2%) of pure glycerin (according to the number of OH). Fatty acid nitriles thus added are placed in a reactor equipped with a gas transmission tube, a blender, an internal thermometer and a condensation system, and 2% by weight sodium dodecylbenzenesulfonate is added. Ammonia is passed through the reaction mixture at the rate of 60 l kg of the reaction mixture at 1 h at 290 ° C. Water formed in the course of the reaction is all that time. Reaction time is 1 h. After distilling the contents of the reactor, 415 g of itryl fatty acid of animal fat is obtained (yield 93.1 %) containing amides. EXAMPLE 18. In each experiment under the conditions described in Example 17, it was subjected. The processing of 500 grams of the technical animal sioapa of the lower grades (the coefficient of saponification is 194.8, the acid number is 0.45). The amount of released glycerin after 3 hours at 230 ° C is 67%. The results of experiments using different catalysts are given in table. 3. PRI me R 19. The reaction is carried out in a 1000 ml heated reactor equipped with a gas transmission tube, a stirrer, a thermometer for the reaction mass and a condensation system (Example 16). The reactor is filled with triglyceride or monoglyceride in the amounts indicated in the table. 2, and 2 wt.% Catalyst. During each reaction, ammonia is passed through the reaction mixture at a rate of 600 l per 1 kg of glyceride per hour. First, the reaction temperature is maintained at 230 ° C for 3 hours and then increased every half hour by 10 ° C. At 270 ° C, the reaction complete. Aqueous extraction at 80-90 ° C carried out the separation of the condensed mixture of products into phases - nitrile fatty acids and: glycerin-VO yes. The content of amides and fatty acids in the thus obtained nitrile of fatty acids, the yield of nitrile and crude glycerol are given for each experiment in Table 4. The fatty acid nitrile introduced in each experiment is placed in a reactor equipped with a gas transmission tube, a stirrer, a thermometer for the reaction mixture and a condenser system, and 1 wt.% Of zinc dodecyl benzene sulfonate is charged. At 290 ° C, ammonia is passed through the reaction mixture for 2 hours at a rate of 150 liters per kg of reaction mixture per hour. At the same time, water formed during the reaction is removed by a gas stream. Upon completion of the reaction, the products are again distilled. Fatty acid nitriles thus obtained contain about 0.1 wt.9 & fatty acids and about 0.2 wt.% amides. Example 20. In the reaction apparatus described in example 16, load 480 g of zinc tristearate with 2 wt.% Zinc stearate in the calculation of glycerin. The reaction is carried out by passing ammonia in the calculation of 600 l per I kg of glycerin per hour. The reaction temperature is 250 ° C. After 4.5 h, the reaction is complete. Volatile reaction products are introduced into the condensation system. The reaction mixture is then separated by aqueous extraction into phases — stearic acid nitrile and glycerin-water. The nitrile injected contains 6.2% by weight amide in 1.5% by weight fatty acid. The yield of stearic acid nitrile is 90%. The yield of pure glycerol is 81%. Under the conditions of example 19, the nitrile is then further processed and distilled. The nitrile yield is then 87.6%. Stearic acid nitrile contains 0.2 wt.% Amide and 0.2 wt.% Fatty acids.
Temperature in the reactor, ° С
Reaction time, -h
230
230-250
250-260
260-270
270
Table 1
The amount of activated glycerol,% of theoretical,
40
270-290
0.5
290
1.25
Zinc perfluorohexane sulfonate
Zinc isopropyl naphthalene sulfonate
: C J 5 C18 alkanesulfonate
.zinc
Zinc salt of the reaction product of benzene, oleic acid and sulfuric acid.
93.3
95.5
5.25
92.8
95 5.5
table 2
39
78
.37 32
82 83
33
77
Table 3
64
82
0.9
8.3
60
75.2
1.1
10.2
85
6
943
4.5
6.25
91.2
91.8
5.75
2 wt% zinc caprylate6
2 wt.% Zinc erucate5.75
79188,813,11,4
5.4592,890,2931.7
530
91.2 63088,785,9
595393.2
94.7
4.8
Continued table. 3
64
71
1.4
11.7
80.5
63
9.7
1.1
13.4
59
1.7
70
61
753
12.4
1.6
57
71
763
59
1.2
7.5
62
76
14.1
1.7
70
58
93,469
1.5
6.4
65
92.8
1.4
73
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权利要求:
Claims (3)
[1]
fS 17 Claim 1. Method for preparing nitriles of fatty acids of general formula Rj (hjR3) CN or RaGN, where RI, RJ, Ra are alkyl radicals with carbon atoms 3-23, or their mixtures by treating glycerides of general formula CHj - OX CH - OU bNg - OCX) Rj I where X is COR or H; Y is CORs or H; RI. Rif RS have the indicated values, or their mixtures in the liquid phase with gaseous ammonia at a temperature in the presence of a catalyst, followed by separation of the target products, characterized in that, in order to simultaneously obtain glycerin and simplify the process of jB, 1-49 of the salt glyceride is used as catalyst lead, or cadmium, or iron, or cobalt, or zinc mono or dicarboxylic saturated or unsaturated aliphatic acid with 4-24 carbon atoms, benzene- or naphthalenimo fum of dicarboic acid, substituted a radical with 1-12 carbon atoms218 yes, alkane mono or alkane disulfonic acid, benzene or naphthalene monoxyd disulfonic acid substituted with an alkyl radical with 1-12 carbon atoms, or a mixture of these, and the process is carried out when alhiac is fed at a speed of 500-690 g / kg of glyceride per 1 h at 220-300 ° C with subsequent separation of the volatile mixture of TOB products withdrawn from the reaction zone into phases - nitrile {glyu acid and glycerin-water - and isolation of the desired products from them.
[2]
2. The method according to claim 1, that is, that the process is carried out at 220-240 ° C before the glycerin is removed from the reaction zone in an amount of 30-68% by weight of the reaction mass, followed by heating the reaction mixture continuously or stepwise within 0.5-5 hours to 270-300 ° C.
[3]
3. Method according to paragraphs. 1 and 2, that is, the fact that the nitrile phase is subjected to subsequent treatment with ammonia is supplied. with a rate of 150 l / kg h of nitrile at the indicated temperature and catalphator. Sources of information taken into account during the examination 1. Patent of England No. 451594, published. 1936 (prototype). Priority points: 08/28/77 in PP. 1, 2, 03/25/78 under item 3.

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同族专利:

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公开号 | 公开日

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IL55385D0|1978-10-31|

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CA1135722A|1982-11-16|

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AU3907678A|1980-02-21|

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FI63961B|1983-05-31|

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DK367978A|1979-02-21|

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EP0000916B1|1981-05-20|

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ATA600778A|1980-05-15|

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DD138311A5|1979-10-24|

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PL119196B1|1981-12-31|

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JPS6246530B2|1987-10-02|

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RO77028A|1981-06-22|

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PT68440A|1978-09-01|

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AU519437B2|1981-12-03|

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CS202509B2|1981-01-30|

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AR218080A1|1980-05-15|

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BR7805331A|1979-04-24|

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NO147271C|1983-03-16|

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EG13422A|1981-12-31|

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IE781677L|1979-02-20|

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EP0000916A1|1979-03-07|

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FI782516A|1979-02-21|

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TR20021A|1980-07-01|

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IN150312B|1982-09-11|

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US4234509A|1980-11-18|

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HK8184A|1984-02-10|

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AT359991B|1980-12-10|

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DK159064C|1991-01-21|

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IT7826849D0|1978-08-18|

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GR73064B|1984-01-30|

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PH16609A|1983-11-24|

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SG37883G|1984-02-17|

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BG33734A3|1983-04-15|

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IE47316B1|1984-02-22|

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HU180472B|1983-03-28|

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JPS5441806A|1979-04-03|

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ES472553A1|1979-02-16|

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IL55385A|1982-02-28|

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FI63961C|1983-09-12|

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MY8500553A|1985-12-31|

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DE2860715D1|1981-08-27|

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IT1099021B|1985-09-18|

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MX147995A|1983-02-22|

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DK159064B|1990-08-27|

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NO782821L|1979-02-21|

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YU197778A|1983-01-21|

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PL209133A1|1979-05-07|

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NZ188179A|1980-08-26|

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OA06038A|1980-06-30|

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NO147271B|1982-11-29|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE19772737607|DE2737607A1|1977-08-20|1977-08-20|Fatty acid nitrile and glycerol prodn. - by reacting mono, di, or tri:glyceride with ammonia in liq. phase at elevated temp. in presence of catalyst|

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DE19782813204|DE2813204A1|1978-03-25|1978-03-25|Simultaneous prepn. of fatty acid nitrile and glycerol - by catalytically contacting glyceride, esp. natural fats and oils, with ammonia|

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