CN101920196B - Hydrogenation catalyst for synthesizing neotame and preparation method thereof - Google Patents
Hydrogenation catalyst for synthesizing neotame and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrogenation catalyst for synthesizing neotame and a preparation method thereof, and the method comprises the following steps: carrying out treatment on activated carbon by using dilute nitric acid solution to obtain the carrier activated carbon; and dissolving palladium chloride in concentrated hydrochloric acid and distilled water, then mixing the solution with the carrier activated carbon, adding water solution of formaldehyde, further adding sodium hydroxide solution for basification, washing with water till no chlorion, and drying to obtain the hydrogenation catalyst for synthesizing the neotame. The hydrogenation catalyst for synthesizing the neotame has high activity and high hydrogenation productivity, the preparation method is simple, the catalyst can be recycled after the treatment, metal palladium can be recycled, and the using cost is low.
Description
Technical field
The invention belongs to the food additives field, be specifically related to a kind of hydrogenation catalyst for synthesizing neotame and preparation method thereof.
Background technology
Knob is sweet to be a kind of novel powerful sweetener, is the derivative of Aspartame, its chemistry N-[N-(3, the 3-dimethylbutyl)] by name-L-a-asparagine-L-phenylalanine-1-methyl esters.Knob is sweet to have good performance; Cost performance is high, is used 2003 as food additives by a plurality of countries and regions approval such as the U.S., European Union, Japan; China Ministry of Public Health also ratifies sweet can the measuring on demand as sweetener of knob and adds in the varieties of food items, and its range of application very extensively.
The synthetic method that knob is sweet is existing multiple, and these methods respectively have advantage, but also exists not enough.General method is first with Aspartame and 3, and the 3-dimethyl butyraldehyde forms imines, and it is sweet to obtain knob with the saturated carbon-to-nitrogen double bon of catalytic hydrogenation again.In hydrogenation process, need use hydrogenation catalyst, and the performance of catalyst is very big to the combined coefficient influence.
Hydrogenation catalyst is one type can significantly change hydrogenation speed and itself does not participate in the particular matter of chemical reaction.In catalytic hydrogenation, multiple transition elements all has certain catalytic activity, and with the most use is platinum family element and nickel.Platinum catalyst is the noble metal catalyst of a quasi-representative, the multiple group of ability hydrogenation, and catalytic activity is high, and required reaction condition is gentle, is usually used in the hydrogenation of ethylene linkage, carbonyl, aromatic nitro and aromatic ring, but is not easy to reclaim.Skeleton nickel is a kind of catalyst that has wide range of applications, and almost all functional groups that can carry out hydrogenation is all worked, and is especially quite effective to the hydrogenation of alkene and aromatic ring, but to the hydrogenation poor effect of imines.Rhodium catalyst is a kind of important hydrogenation catalyst, and activity is quite high in acetic aid medium, can hydrogenation under normal temperature, normal pressure phenyl ring, heterocycle, the reduction of ethylene linkage, aromatic nitro and carbonyl is all had activity, but use cost is higher.
Summary of the invention
In order to solve the weak point of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of hydrogenation catalyst for synthesizing neotame.
Another object of the present invention is to provide a kind of hydrogenation catalyst for synthesizing neotame.
The object of the invention is realized through following technical scheme:
A kind of preparation method of hydrogenation catalyst for synthesizing neotame comprises following concrete steps:
(1) in active carbon, adding mass percent concentration is 8～12% dilute nitric acid solution, in steam bath, heats, and adds the clean nitric acid of washing then, oven dry, carrier active carbon;
(2) palladium bichloride, concentrated hydrochloric acid and distilled water are mixed, in steam bath, be heated to the palladium bichloride powder and dissolve fully, get a solution;
(3) in carrier active carbon, add distilled water, stir, be heated to and add a solution behind 78 ℃～82 ℃ constant temperature and mix, b solution;
(4) in b solution, adding mass percent concentration is 13～17% formalin, and then adds sodium hydrate aqueous solution to being alkalescence, continues to stir, and leaves standstill cooled and filtered, and washing is not to there being chlorion, dry hydrogenation catalyst for synthesizing neotame.
The mass volume ratio of said active carbon of step (1) and dilute nitric acid solution is 1: 2; The time of said heating is 2～3 hours; The temperature of said oven dry is 100 ℃～110 ℃.
Preferably, the mass percent concentration of the said dilute nitric acid solution of step (1) is 10%;
The mass volume ratio of the said palladium bichloride of step (2), concentrated hydrochloric acid and distilled water is 1: 3: 8; The mass percent concentration of said concentrated hydrochloric acid is 30～35%.
The mass volume ratio of said carrier active carbon of step (3) and distilled water is 3: 5.
The volume ratio of said formalin of step (4) and b solution is 1: 10.
The mass percent concentration of sodium hydroxide solution is 20% described in the step (4); The time that said continuation is stirred is 1～2 hour; Said washing times is 5～7 times.
Preferably, the mass percent concentration of said formalin is 15%;
Hydrogenation catalyst for synthesizing neotame of the present invention is obtained by above-mentioned preparation method.
The weight content of Metal Palladium is 10% in the above-mentioned hydrogenation catalyst for synthesizing neotame.
Hydrogenation catalyst for synthesizing neotame of the present invention is renewable after handling through hydrochloric acid, salpeter solution, has reduced the use cost of catalyst greatly.
Principle of the present invention is:
For avoiding the over oxidation effect of red fuming nitric acid (RFNA), what when handling active carbon, select for use is that mass percent concentration is rare nitric acid of 8～12%; The concentration of used formaldehyde is influential to catalytic activity, when concentration of formaldehyde is too low, reduces not thoroughly, and simple substance palladium content is on the low side, and catalytic activity is not enough; When concentration of formaldehyde was too high, impurity content increased, and these impurity can make catalyst slightly poison, and catalytic activity reduces, and was that 13～17% formalin is better with mass percent concentration; The process of washed several times with water dechlorination ion is very beneficial to the catalytic activity that improves catalyst.Washing times is not enough, and the existence of small amounts of chlorine ion can be disturbed catalytic process, influences catalytic efficiency.
The present invention compared with prior art has following advantage and beneficial effect:
The active height of hydrogenation catalyst for synthesizing neotame involved in the present invention, hydrogenation productive rate can reach more than 90%, and the preparation method is simple, and renewable after the catalyst treatment, Metal Palladium is recyclable, and use cost is low.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1:
(1) preparing mass percent concentration by red fuming nitric acid (RFNA) is that 12% dilute nitric acid solution is for use; Take by weighing the 20.0g active carbon and join in the round-bottomed flask, adding 40mL mass percent concentration is rare nitric acid of 12%, in steam bath, heats 2h, washes nitric acid then, 100 ℃ of oven dry, gets carrier active carbon, and is for use; Take by weighing the 1.0g palladium bichloride and join in the round-bottomed flask, adding 3mL mass percent concentration is 30% concentrated hydrochloric acid and 8mL distilled water, in steam bath, is heated to the palladium bichloride powder and dissolves fully, gets a solution; The 12.0g carrier active carbon is joined in the beaker, add 20mL distilled water, the quick stirring is heated to 78 ℃, and constant temperature adds a solution and mixes, and washs round-bottomed flask 2 times with a little distilled water, and cleaning solution is transferred in the beaker, obtains b solution; Adding 2mL mass percent concentration is 13% formalin in b solution; Drip mass percent concentration then and be 20% sodium hydrate aqueous solution and be alkalescence to using litmus paper to detect; Continue to stir 1h, leave standstill cold filtration, wash 5 times till do not have a chlorion; In air, place the drier that fills potassium hydroxide or anhydrous calcium chloride dry then, promptly get hydrogenation catalyst for synthesizing neotame, wherein the weight content of Metal Palladium is 10%.
(2) in autoclave, add 20.0g (0.068mol) Aspartame, 100.0g methyl alcohol, add 1.0g 10% hydrogenation catalyst for synthesizing neotame and 6.7g (0.067mol) 3 again, the 3-dimethyl butyraldehyde; Stir with 450rps speed,, drive away nitrogen 4 times with hydrogen again with nitrogen flooding deacration 4 times; And keep 0.5Mpa pressure, and be warming up to 40 ℃, stir with 1000rps speed; Reacted 6 hours, and after reaction stops, removing hydrogen with nitrogen flooding; Question response liquid is cooled to suction filtration after the room temperature, and filter cake washs with 50mL distilled water; Filtrating is placed on refrigerator overnight, crystallization, suction filtration, white solid, with methyl alcohol and water mixed solvent be recrystallized white crystal 23.0g, productive rate 87.4%, 82～84 ℃ of fusing points.
Embodiment 2:
(1) preparing mass percent concentration by red fuming nitric acid (RFNA) is that 8% dilute nitric acid solution is for use; Take by weighing the 20.0g active carbon and join in the round-bottomed flask, adding 40mL mass percent concentration is rare nitric acid of 8%, in steam bath, heats 2.5h, washes nitric acid then, 105 ℃ of oven dry, gets carrier active carbon, and is for use; Take by weighing the 1.0g palladium bichloride and join in the round-bottomed flask, adding 3mL mass percent concentration is 35% concentrated hydrochloric acid and 8mL distilled water, in steam bath, is heated to the palladium bichloride powder and dissolves fully, gets a solution; The 12.0g carrier active carbon is joined in the beaker, add 20mL distilled water, the quick stirring is heated to 82 ℃, and constant temperature adds a solution and mixes, and washs round-bottomed flask 2 times with a little distilled water, and cleaning solution is transferred in the beaker, obtains b solution; Adding 2mL mass percent concentration is 17% formalin in b solution; Drip mass percent concentration then and be 20% sodium hydrate aqueous solution and be alkalescence to using litmus paper to detect; Continue to stir 1h, leave standstill cold filtration, wash 6 times till do not have a chlorion; In air, place the drier that fills potassium hydroxide or anhydrous calcium chloride dry then, promptly get hydrogenation catalyst for synthesizing neotame, wherein the weight content of Metal Palladium is 10%.
(2) in autoclave, add 20.0g (0.068mol) Aspartame, 100.0g methyl alcohol, add 1.0g 10% hydrogenation catalyst for synthesizing neotame and 6.7g (0.067mol) 3 again, the 3-dimethyl butyraldehyde; Stir with 450rps speed,, drive away nitrogen 4 times with hydrogen again with nitrogen flooding deacration 4 times; And keep 0.5Mpa pressure, and be warming up to 40 ℃, stir with 1000rps speed; Reacted 6 hours, and after reaction stops, removing hydrogen with nitrogen flooding; Question response liquid is cooled to suction filtration after the room temperature, and filter cake washs with 50mL distilled water; Filtrating is placed on refrigerator overnight, crystallization, suction filtration, white solid, with methyl alcohol and water mixed solvent be recrystallized white crystal 23.6g, productive rate 89.7%, 82～84 ℃ of fusing points.
The comparative example 1:
(1) preparing mass percent concentration by red fuming nitric acid (RFNA) is that 10% dilute nitric acid solution is for use; Take by weighing the 20.0g active carbon and join in the round-bottomed flask, adding 40mL mass percent concentration is rare nitric acid of 10%, in steam bath, heats 3h, washes nitric acid then, 110 ℃ of oven dry, gets carrier active carbon, and is for use; Take by weighing the 1.0g palladium bichloride and join in the round-bottomed flask, adding 3mL mass percent concentration is 35% concentrated hydrochloric acid and 8mL distilled water, in steam bath, is heated to the palladium bichloride powder and dissolves fully, gets a solution; The 12.0g carrier active carbon is joined in the beaker, add 20mL distilled water, the quick stirring is heated to 80 ℃, and constant temperature adds a solution and mixes, and washs round-bottomed flask 3 times with a little distilled water, and cleaning solution is transferred in the beaker, obtains b solution; Adding 2mL mass percent concentration is 15% formalin in b solution; Drip mass percent concentration then and be 20% sodium hydrate aqueous solution and be alkalescence to using litmus paper to detect; Continue to stir 2h, leave standstill cold filtration, wash 7 times till do not have a chlorion; In air, place the drier that fills potassium hydroxide or anhydrous calcium chloride dry then, promptly get hydrogenation catalyst for synthesizing neotame, wherein the weight content of Metal Palladium is 10%.
(2) in autoclave, add 20.0g (0.068mol) Aspartame, 100.0g methyl alcohol, add 1.0g 10% hydrogenation catalyst for synthesizing neotame and 6.7g (0.067mol) 3 again, the 3-dimethyl butyraldehyde; Stir with 450rps speed,, drive away nitrogen 4 times with hydrogen again with nitrogen flooding deacration 4 times; And keep 0.5Mpa pressure, and be warming up to 40 ℃, stir with 1000rps speed; Reacted 6 hours, and after reaction stops, removing hydrogen with nitrogen flooding; Question response liquid is cooled to suction filtration after the room temperature, and filter cake washs with 50mL distilled water; Filtrating is placed on refrigerator overnight, crystallization, suction filtration, white solid, with methyl alcohol and water mixed solvent be recrystallized white crystal 24.0g, productive rate 91.2%, 82～84 ℃ of fusing points.
(3) in autoclave, add 20.0g (0.068mol) Aspartame, 100.0g methyl alcohol, add 2.0g 5%Pa/C (usual method preparation) and 6.7g (0.067mol) 3 again, the 3-dimethyl butyraldehyde; Stir with 450rps speed,, drive away nitrogen 4 times with hydrogen again with nitrogen flooding deacration 4 times; And keep 0.5Mpa pressure, and be warming up to 40 ℃, stir with 1000rps speed; Reacted 6 hours, and after reaction stops, removing hydrogen with nitrogen flooding; Question response liquid is cooled to suction filtration after the room temperature, and filter cake washs with 50mL distilled water; Filtrating is placed on refrigerator overnight, crystallization, suction filtration, white solid, with methyl alcohol and water mixed solvent be recrystallized white crystal 20.0g, productive rate 76.0%, 82～84 ℃ of fusing points.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. the preparation method of a hydrogenation catalyst for synthesizing neotame is characterized in that comprising following concrete steps:
(1) in active carbon, adding mass percent concentration is 8～12% dilute nitric acid solution, in steam bath, heats, and adds the clean nitric acid of washing then, oven dry, carrier active carbon;
(2) palladium bichloride, concentrated hydrochloric acid and distilled water are mixed, in steam bath, be heated to the palladium bichloride powder and dissolve fully, get a solution;
(3) in carrier active carbon, add distilled water, stir, be heated to and add a solution behind 78 ℃～82 ℃ constant temperature and mix, b solution;
(4) in b solution, adding mass percent concentration is 13～17% formalin; The volume ratio of said formalin and b solution is 1: 10; And then add sodium hydrate aqueous solution to being alkalescence, and continue to stir, leave standstill cooled and filtered; Washing is to not having chlorion, the dry hydrogenation catalyst for synthesizing neotame that gets.
2. the preparation method of a kind of hydrogenation catalyst for synthesizing neotame according to claim 1, it is characterized in that: the mass volume ratio of said active carbon of step (1) and dilute nitric acid solution is 1g: 2ml.
3. the preparation method of a kind of hydrogenation catalyst for synthesizing neotame according to claim 1, it is characterized in that: the mass percent concentration of the said dilute nitric acid solution of step (1) is 10%; The time of said heating is 2～3 hours; The temperature of said oven dry is 100 ℃～110 ℃.
4. the preparation method of a kind of hydrogenation catalyst for synthesizing neotame according to claim 1, it is characterized in that: the mass volume ratio of the said palladium bichloride of step (2), concentrated hydrochloric acid and distilled water is 1g: 3ml: 8ml; The mass percent concentration of said concentrated hydrochloric acid is 30～35%.
5. the preparation method of a kind of hydrogenation catalyst for synthesizing neotame according to claim 1, it is characterized in that: the mass volume ratio of said carrier active carbon of step (3) and distilled water is 3g: 5ml.
6. the preparation method of a kind of hydrogenation catalyst for synthesizing neotame according to claim 1, it is characterized in that: the mass percent concentration of sodium hydroxide solution is 20% described in the step (4); The mass percent concentration of said formalin is 15%; The time that said continuation is stirred is 1～2 hour; Said washing times is 5～7 times.
7. hydrogenation catalyst for synthesizing neotame, each said preparation method obtains by claim 1～6.
8. a kind of hydrogenation catalyst for synthesizing neotame according to claim 7 is characterized in that: the weight content of Metal Palladium is 10% in the said hydrogenation catalyst for synthesizing neotame.
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| CN100432097C (en) * | 2006-11-16 | 2008-11-12 | 暨南大学 | Synthetic methods for nutame |
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