CN102516131B - Synthesis method of food grade modified foaming agent azodicarbonamide - Google Patents
Synthesis method of food grade modified foaming agent azodicarbonamide Download PDFInfo
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- CN102516131B CN102516131B CN 201110329254 CN201110329254A CN102516131B CN 102516131 B CN102516131 B CN 102516131B CN 201110329254 CN201110329254 CN 201110329254 CN 201110329254 A CN201110329254 A CN 201110329254A CN 102516131 B CN102516131 B CN 102516131B
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Abstract
The invention discloses a synthesis method of food grade modified foaming agent azodicarbonamide. Biurea is used as as raw material, and under the effect of a cerium composite catalyst and a reaction solvent, the temperature of the solution is adjusted to 60-70 DEG, the pH value is 2-5, catalytic oxidation reaction is carried out for 3-5h under the oxygen condition, and then the food grade modified foaming agent azodicarbonamide can be obtained through filtering and purifying. The synthesis method disclosed by the invention has a novel process, low requirements on reaction equipment, and is environment-friendly and safe. A product obtained by the method contains fewer impurities, has good quality and high yield, and can be used in food-grade additives.
Description
Technical field
The present invention relates to a kind of synthetic method of Cellmic C 121, be specifically related to a kind of synthetic method of modified foaming agent Cellmic C 121.
Background technology
Hydrazo-dicarbonamide: its chemical formula is C
2H
6N
4O
2, English name is 1,2-Hydrazinedicarboxamide, structural formula is
, Cellmic C 121, its English name are Azodicarbonamide, structural formula is:
, Cellmic C 121 is commonly called as " AC " whipping agent, can be used as normal pressure or the pressure expansion agent of products such as polyvinyl chloride, chloroprene rubber, natural rubber, is a kind of application whipping agent very widely.The nontoxic odorless of " AC " whipping agent, high temperature easily decomposes gases such as discharging nitrogen, it also is a kind of outstanding flour improver, the dough that added " AC " whipping agent is more dried, force of cohesion is big, has changed the rheologic behavio(u)r of dough, makes the loaf volume of making big, quality, outward appearance, formability are all fine, therefore most of American-European countries such as American and Britain, method, moral, day, meaning etc. all permission " AC " whipping agent use as foodstuff additive.
Being in great demand of " AC " whipping agent whole world, a kind of is to use as plastics blowing agent, another kind is to use as foodstuff additive.At present both at home and abroad the synthetic production method of " AC " whipping agent all continue to use decades ago the synthetic production method of technical grade " AC " whipping agent, its processing method all is to be condensed into hydrazo-dicarbonamide with hydrazine hydrate and urea heating earlier in sour environment, synthesizing of hydrazo-dicarbonamide is simple, and yield is also high.Second step was with hydrazo-dicarbonamide oxidation preparation " AC " whipping agent, and according to the difference of oxygenant, processing method is difference to some extent also, and the yield of resulting quality product and product is also slightly different, and available oxygenant has chlorine, hydrogen peroxide, nitric acid, oxymuriate.Chlorine toxicity is quite big, and corrodibility is strong, and is quite high to equipment requirements; The oxidisability of nitric acid is strong, and corrodibility is strong, and is all very big to the corrodibility of equipment, equally with chlorine has a more serious potential safety hazard; The hydrogen peroxide concentration too yield of low production is on the low side, influences production cost, and concentration is too high to cause an explosion accident easily; The enterprise that produces " AC " whipping agent both at home and abroad adopts chlorate process more now, also has oxymuriate is mixed use as oxygenant with hydrogen peroxide.Adopt the reaction formula of oxygenant oxidation hydrazo-dicarbonamide preparation " AC " whipping agent as follows:
Chlorate process (also can be called the chloric acid method, so processing condition requiring to acid) uses more, and as J7898926, Ger (East) 13.370, U.S.3227706, J7118735 etc. have all adopted the chloric acid method, and state of the art is higher relatively.On producing, the chloric acid method to the requirement of acidity than higher, and with adopt nitric acid, other technology that chlorine, hydrogen peroxide etc. are made oxygenant is the same, has problems such as production security difference.In a word, the technology that adopts strong oxidizer oxidation hydrazo-dicarbonamide to produce " AC " agent all exists technology outmoded, and the equipment requirements height is all very big to the harm of human and environment, will progressively be lost the market competitiveness as not improving and improving.
" AC " whipping agent of explained hereafter such as employing chlorate process, be difficult to remove because containing the hypertoxicity impurity atom, and under the effect of strong oxidizers such as chloric acid, generate a large amount of oxidisability assorted be difficult to purify remove, have a strong impact on the quality of " AC " whipping agent, therefore " AC " whipping agent of producing with this method can only be used as the whipping agent use of products such as plastics, can not be used for foodstuff additive.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of modified foaming agent Cellmic C 121, this synthetic method does not adopt chlorine, hydrogen peroxide, nitric acid, strong oxidizers such as oxymuriate, technology is new, less demanding to conversion unit, Environmental Safety, the impurity that the product that adopts this method to obtain contains is few, can be used for food grade additives.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of synthetic method of food grade modified foaming agent Cellmic C 121, be raw material with the hydrazo-dicarbonamide, under the effect of cerium composite catalyst and reaction solvent, the regulator solution temperature is that 60-70 ℃, pH value can prepare the modified foaming agent Cellmic C 121 for 2-5 carries out catalytic oxidation 3-5h under logical oxygen condition by filtering to purify.
Cerium composite catalyst consumption of the present invention preferably accounts for the 15-80% of hydrazo-dicarbonamide total mass.
Cerium composite catalyst of the present invention comprises support of the catalyst and catalyst activity composition, described catalyst activity composition consumption accounts for the 2.5-12% of support of the catalyst total mass, wherein support of the catalyst is preferably macromolecular cpd, and described catalyst activity composition is preferably the high price cerium compound.
High price cerium compound of the present invention preferably includes ceric sulfate and/or the cerium dioxide that contains crystal water.
Macromolecular cpd of the present invention preferably includes the macromole silicate that contains the alkylsulphonic acid base.Its effect is identical a bit with molecular sieve and macroporous resin, thereby if but use molecular sieve or macroporous resin often by superfine Cellmic C 121 powder wrapped catalyst active center cause catalytic activity to descend, so conventional support of the catalyst effect is bad, preferably adopts the support of the catalyst among the present invention.
And the cerium composite catalyst that adopts among the present invention can activatedly use repeatedly, detailed process can preferably adopt following technique means: get the catalyzer 100g that access times surpass 30 times, the hydrazine hydrate that adds 200mL 5% soaked 6 hours, clean to elutant with 3% dilute sulphuric acid again and be acid, 2.g cerium dioxide, add in 200ml 18% sulfuric acid, soaked 12 hours at 45 ℃, filtering with pH is that 2.5 dilute sulphuric acid washs and can re-use for 2 times.
The macromole silicate that contains the alkylsulphonic acid base of the present invention prepares by the following method: get dodecyl sodium sulfonate potassium, water glass, zinc bromide mixing, added the abundant stirring reaction of deionized water 30 ~ 48 hours, add again and leave standstill after Manganse Dioxide fully mixes, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, high-temperature calcination namely prepares the macromole silicate that contains the alkylsulphonic acid base then.
The mass ratio of dodecyl sodium sulfonate potassium of the present invention, water glass, zinc bromide is 0.5-0.75:1.0:0.01-0.015, the consumption of water is dodecyl sodium sulfonate potassium, water glass and zinc bromide total mass 2-5 times, and the consumption of manganese dioxide powder accounts for the 1.8-3.6% of dodecyl sodium sulfonate potassium, water glass and zinc bromide total mass.
Temperature during high-temperature calcination of the present invention is 650-1000 ℃.
Reaction solvent of the present invention is water, and its volume mass ratio with hydrazo-dicarbonamide is 4.0-6.0mL:1.0g.
The detailed process of purification of the present invention is: the solution behind the catalytic oxidation is filtered, get filter residue through washing 1-5 time, namely obtain the modified foaming agent Cellmic C 121 of food grade 50-70 ℃ of drying.
The present invention has following advantage:
(1) the present invention directly adopts airborne oxygen as catalyzer, adopts the chlorine in the existing technology, hydrogen peroxide, and nitric acid, strong oxidizers such as oxymuriate, thus can solve the residual problem in product of strong oxidizer in the prior art;
(2) synthetic method craft of the present invention is new, and is less demanding to conversion unit, Environmental Safety;
(3) impurity that contains of the product that adopts the inventive method to obtain is few, good product quality, and the yield height can be used for food grade additives.
Embodiment
The invention will be further described below in conjunction with embodiment, but they are not limitation of the invention, and the raw material that wherein adopts is commercially available as there not being special indicating.
Embodiment 1
The macromole silicate that carrier macromolecular cpd in the cerium composite catalyst contains the alkylsulphonic acid base adopts following method to prepare: get dodecyl sodium sulfonate potassium 125g, water glass 200g, zinc bromide 2.5g mixing, adding the 800mL deionized water fully stirred 48 hours, add 6.5g Manganse Dioxide (powder again, particle diameter is 300 orders) fully leave standstill after the mixing, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, in retort furnace, 850 ℃ of high-temperature calcinations namely prepare the macromole silicate that contains the alkylsulphonic acid base then.
Get the above-mentioned macromole silicate of 200g, the 5.0g cerium dioxide adds in the 200mL18% sulfuric acid, soaks 12 hours at 45 ℃, and filtering with pH is namely to prepare the cerium composite catalyst after 2.5 dilute sulphuric acid washs 2 times.
In 1000 milliliters of there-necked flasks, add 500 ml waters, hydrazo-dicarbonamide 120 grams, add cerium composite catalyst 25 grams again, heat to 65 degree, and lasting bubbling air, slowly drip sulfuric acid and keep reaction solution pH=2 ~ 3, react and finish reaction after 4 hours, filter filter cake with three washings of 100 milliliters of moisture, get product 112 grams in 60 degree vacuum-dryings, through IR, 1H-NMR and its structure of ESI-MS analysis confirmation are Cellmic C 121, yield 94.9%; Content is greater than 99.5%, and detection method is with reference to HG2097-2008.
Embodiment 2
The macromole silicate that carrier macromolecular cpd in the cerium composite catalyst contains the alkylsulphonic acid base adopts following method to prepare: get dodecyl sodium sulfonate potassium 100g, water glass 200g, zinc bromide 2g mixing, adding the 610mL deionized water fully stirred 30 hours, add 5.5g Manganse Dioxide (powder again, particle diameter is 300 orders) fully leave standstill after the mixing, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, in retort furnace, 650 ℃ of high-temperature calcinations namely prepare the macromole silicate that contains the alkylsulphonic acid base then.
Get the above-mentioned macromole silicate of 200g, the 10g cerium dioxide adds in the 200mL18% sulfuric acid, soaks 12 hours at 45 ℃, and filtering with pH is namely to prepare the cerium composite catalyst after 2.5 dilute sulphuric acid washs 2 times.
In 1000 milliliters of there-necked flasks, add 500mL water, add 100 gram hydrazo-dicarbonamides, and adjust its pH value to 2.5,30 gram cerium composite catalysts, heat to 60 ℃, and lasting bubbling air, slowly drip sulfuric acid and keep reaction solution pH=2.5, react and finish reaction after 3 hours, filter filter cake with three washings of 100 milliliters of moisture, get 108 gram products 50 ℃ of vacuum-dryings, through IR, 1H-NMR and its structure of ESI-MS analysis confirmation are Cellmic C 121, yield is 91.5%, and content is greater than 99.5%, and detection method is with reference to HG2097-2008.
Embodiment 3
The macromole silicate that carrier macromolecular cpd in the cerium composite catalyst contains the alkylsulphonic acid base adopts following method to prepare: get dodecyl sodium sulfonate potassium 150g, water glass 200g, zinc bromide 3g mixing, adding the 1765mL deionized water fully stirred 40 hours, add 12.7g Manganse Dioxide (powder again, particle diameter is 300 orders) fully leave standstill after the mixing, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, in retort furnace, 1000 ℃ of high-temperature calcinations namely prepare the macromole silicate that contains the alkylsulphonic acid base then.
Get the above-mentioned macromole silicate of 200g, the 24g cerium dioxide adds in the 200mL18% sulfuric acid, soaks 12 hours at 45 ℃, and filtering with pH is namely to prepare the cerium composite catalyst after 2.5 dilute sulphuric acid washs 2 times.
In 1000 milliliters of there-necked flasks, add 600mL water, and adjust its pH value to 2, add 100 gram connection ureas, the above-mentioned cerium composite catalyst of 40 grams, heat to 70 ℃, and lasting bubbling air, slowly dripping sulfuric acid maintenance reaction solution pH is 5, react and finish reaction after 5 hours, filter filter cake with three washings of 100 milliliters of moisture, get 113 gram products 70 ℃ of vacuum-dryings, through IR, 1H-NMR and its structure of ESI-MS analysis confirmation are Cellmic C 121, yield is 95.7%, and content is greater than 99.5%, and detection method is with reference to HG2097-2008.
Embodiment 4
The macromole silicate that carrier macromolecular cpd in the cerium composite catalyst contains the alkylsulphonic acid base adopts following method to prepare: get dodecyl sodium sulfonate potassium 125g, water glass 200g, zinc bromide 2.5g mixing, adding the 800mL deionized water fully stirred 48 hours, add 6.5g Manganse Dioxide (powder again, particle diameter is 300 orders) fully leave standstill after the mixing, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, in retort furnace, 850 ℃ of high-temperature calcinations namely prepare the macromole silicate that contains the alkylsulphonic acid base then.
Get the above-mentioned macromole silicate of 200g, the 5.0g cerium dioxide adds in the 200mL18% sulfuric acid, soaks 12 hours at 45 ℃, and filtering with pH is namely to prepare the cerium composite catalyst after 2.5 dilute sulphuric acid washs 2 times.
In 1000 milliliters of there-necked flasks, add 500mL water, and adjust its pH value to 3, add 100 gram connection ureas, 80 gram composite catalysts, reaction conditions and other operation are identical with embodiment 1, get 112 gram Cellmic C 121s, yield 94.9%, content is greater than 99.5%.
Embodiment 5
Get the catalyzer 100g that access times surpass 30 times, the hydrazine hydrate that adds 200mL 5% soaked 6 hours, clean to elutant with 3% dilute sulphuric acid again and be acid, 2.g cerium dioxide, add in 200ml 18% sulfuric acid, soaked 12 hours at 45 ℃, filtering with pH is that 2.5 dilute sulphuric acid washs and can re-use for 2 times.
In 1000 milliliters of there-necked flasks, add 500 ml waters, hydrazo-dicarbonamide 120 grams add above-mentioned through bringing back to life cerium composite catalyst 25 grams of handling reason again, heat to 65 ℃, and lasting bubbling air, slowly drip sulfuric acid and keep reaction solution pH=2 ~ 3, react and finish reaction after 4 hours, filtering filter cake washs for three times with 100 milliliters of moisture, get Cellmic C 121 113 grams 60 ℃ of vacuum-dryings, yield is higher than 90%, and content is greater than 99.5%.
Above embodiment only is used for setting forth the present invention, and protection scope of the present invention is not only to be confined to above embodiment.The those of ordinary skill of described technical field all can be realized purpose of the present invention according to above content disclosed by the invention and scope that each parameter is got.
Claims (2)
1. the synthetic method of a food grade modified foaming agent Cellmic C 121, it is characterized in that: be raw material with the hydrazo-dicarbonamide, under the effect of cerium composite catalyst and reaction solvent, the regulator solution temperature is that 60-70 ℃, pH value can prepare the modified foaming agent Cellmic C 121 for 2-5 carries out catalytic oxidation 3-5h under logical oxygen condition by filtering to purify;
Described cerium composite catalyst comprises support of the catalyst and catalyst activity composition, described catalyst activity composition consumption accounts for the 2.5-12% of support of the catalyst total mass, wherein support of the catalyst is macromolecular cpd, and described catalyst activity composition is the high price cerium compound;
Described reaction solvent is water, and its volume mass ratio with hydrazo-dicarbonamide is 4.0-6.0mL:1.0g.
2. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 1, it is characterized in that: described cerium composite catalyst consumption accounts for the 15-80% of hydrazo-dicarbonamide total mass.
3. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 1, it is characterized in that: described high price cerium compound comprises ceric sulfate and/or the cerium dioxide that contains crystal water.
4. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 1, it is characterized in that: described macromolecular cpd comprises the macromole silicate that contains the alkylsulphonic acid base.
5. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 4, it is characterized in that: the described macromole silicate that contains the alkylsulphonic acid base prepares by the following method: get dodecyl sodium sulfonate potassium, water glass, zinc bromide mixing, added the abundant stirring reaction of deionized water 30 ~ 48 hours, add again and leave standstill after Manganse Dioxide fully mixes, remove water layer and get gel shape thing, allow gel shape thing be deposited as piece, natural air drying, high-temperature calcination namely prepares the macromole silicate that contains the alkylsulphonic acid base then.
6. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 5, it is characterized in that: the mass ratio of described dodecyl sodium sulfonate potassium, water glass, zinc bromide is 0.5-0.75:1.0:0.01-0.015, the consumption of water is dodecyl sodium sulfonate potassium, water glass and zinc bromide total mass 2-5 times, and the consumption of manganese dioxide powder accounts for the 1.8-3.6% of dodecyl sodium sulfonate potassium, water glass and zinc bromide total mass.
7. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 5, it is characterized in that: the temperature during high-temperature calcination is 650-1000 ℃.
8. the synthetic method of food grade modified foaming agent Cellmic C 121 according to claim 1, it is characterized in that: the detailed process of described purification is: the solution behind the catalytic oxidation is filtered, get filter residue through washing 1-5 time, namely obtain the modified foaming agent Cellmic C 121 of food grade 50-70 ℃ of drying.
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| CN103146178B (en) * | 2013-03-22 | 2014-08-20 | 淄博正华发泡材料有限公司 | Chemical polyurethane foaming agent and preparation method thereof |
| CN106008279A (en) * | 2016-05-26 | 2016-10-12 | 江苏索普化工股份有限公司 | Method for preparing azodicarbonamide by oxygen oxidation |
| CN114672062B (en) * | 2022-03-25 | 2023-05-26 | 南京工程学院 | Modified foaming agent and microcellular foaming styrene thermoplastic elastomer |
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Address after: 510308 No. 146 East Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee after: Guangdong Food Industry Research Institute Co Ltd Address before: 510308 No. 146 East Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee before: Guangdong Prov. Food Industry Inst. |
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