CN101857541A - Method for preparing potassium cinnamate - Google Patents
Method for preparing potassium cinnamate Download PDFInfo
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- CN101857541A CN101857541A CN 201010190471 CN201010190471A CN101857541A CN 101857541 A CN101857541 A CN 101857541A CN 201010190471 CN201010190471 CN 201010190471 CN 201010190471 A CN201010190471 A CN 201010190471A CN 101857541 A CN101857541 A CN 101857541A
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Abstract
The invention discloses a method for preparing potassium cinnamate, which comprises the following steps of: A, mixing silver and palladium, dripping nitric acid, raising the temperature, adding carbon powder into the filter liquor in a molar ratio of the silver to the palladium to the carbon powder, regulating the pH value of the solution by using KOH, and obtaining a filter cake, namely a mixture of silver oxide, palladium hydroxide and carbon powder; B, adding aqueous solution of KOH into the mixture of silver oxide, palladium hydroxide and carbon powder in a ratio of the mixture to the aqueous solution of KOH, reducing the temperature, dripping aqueous solution of formaldehyde, reacting, filtering the materials, washing with water to neutral, and drying; C, adding a silver/palladium/carbon catalyst into the solution of potassium hydroxide, stirring to mix the materials, raising the temperature of the materials, introducing pure oxygen, regulating the temperature of the materials, and obtaining aqueous solution of potassium cinnamate; and D, filtering the aqueous solution of potassium cinnamate, wherein the obtained filter cake is the silver/palladium/carbon catalyst, reducing the temperature, crystallizing, performing centrifugal drying, and performing vacuum drying to obtain the finished product of the potassium cinnamate. The method for preparing the potassium cinnamate has the advantages of simple and convenient method, low cost, high yield of 95.9 percent, no environmental pollution, and suitability for industrial production.
Description
Technical field
The invention belongs to the food preservatives field, relate to a kind of preparation method of potassium cinnamate, particularly a kind of catalyzed oxidation preparation method of potassium cinnamate.
Background technology
The chemical name of potassium cinnamate is a 3-cinnamylic acid potassium, have that solvability is good, antimicrobial spectrum is wide, characteristics such as safe in utilization, health care, be a kind of worth further investigation exploitation and the novel natural food preservative of wideling popularize application, be widely used in medicine, agricultural and the food, the domestic and international market is good, and development prospect is tempting.
The preparation potassium cinnamate mainly contains following several method at present:
1, by styracin and wet chemical reaction, gets through concentrating oven dry.The advantage of this method is that operation is simple, but produces a large amount of bubbles in the reaction process, be unfavorable for the control of reacting and the aftertreatment of product, and product yield is on the low side, and raw materials used cost is higher, is unfavorable for suitability for industrialized production.
2, carrying out neutralization reaction by the styracin and the KOH aqueous solution can get.The advantage of this method is that operation is simple, and shortcoming is that raw materials used cost is higher.
Summary of the invention
The objective of the invention is to remedy the deficiency of above-mentioned prior art, a kind of preparation method of potassium cinnamate is provided, this method is easy, and is easy to operate, and raw materials cost is cheap, yield is higher, environmentally safe, be suitable for suitability for industrialized production.
The technical scheme that realizes the object of the invention is:
A kind of preparation method of potassium cinnamate, this method may further comprise the steps:
(1), silver, palladium are pressed 3: the mixed in molar ratio of 2-3, adding excessive concentrations is the nitric acid of 96-98%, is warming up to 90～95 ℃ after dropwising, and stirs 2-3 hour, after silver, palladium are dissolved fully, filter, in filtrate by silver, palladium, carbon dust mol ratio 3: 2-3: 40-50 adds carbon dust, is 10～12 with KOH (only introducing potassium ion) regulator solution pH value, continue to stir 55-65 minute, the carrier carbon dust is fully adsorbed, filter, the gained filter cake is silver suboxide, palladium hydroxide and toner mixture;
(2), the mixture that step (1) is obtained, press mixture, 50% (mass percent) KOH aqueous solution mol ratio 1: 4-5 is in silver suboxide, palladium hydroxide and toner mixture, add the KOH aqueous solution of 50% (mass percent), be cooled to 20-30 ℃, remain on 20-30 ℃ and drip formalin, mixture and formaldehyde mole ratio 1: 1-3, dropwise the back and continue reaction 0.5～1 hour,, be washed to neutrality material filtering, oven dry obtains silver/palladium/carbon catalyst then;
(3), in the potassium hydroxide solution of 4～6wt%, add silver/palladium/carbon catalyst, the mass ratio of water is 1: 100～120 in silver/palladium/carbon catalyst and the potassium hydroxide solution, and it is even to be stirred to mixing of materials; Material is warming up to 60～70 ℃, feed purity oxygen, logical oxygen flow speed control is built in 5～8L/min, kept logical oxygen 15～30 minutes, regulating material temperature then is 60～75 ℃, adds phenylacrolein under the condition that keeps above-mentioned logical oxygen flow speed, the mass ratio of phenylacrolein and catalyzer is 1: 0.05～0.1, the dropping time is 3-5 hour, dropwises the back and continues logical oxygen reaction 10～15 minutes, gets the potassium cinnamate aqueous solution;
(4), the potassium cinnamate aqueous solution is filtered, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle use, gained filtrate is cooled to 10～15 ℃, crystallization with KOH (only introducing potassium ion) adjust pH to 9～10, centrifuge dripping, vacuum-drying get the potassium cinnamate finished product.
Advantage of the present invention is:
The inventive method is simple, and raw material is easy to get, and production cost is low, environmentally safe, and the products obtained therefrom steady quality is reliable, and the yield of producing potassium cinnamate is up to 95.9% (in phenylacrolein).
Embodiment
The present invention is further illustrated below by specific embodiment, but protection content of the present invention is not limited to following examples.
If no special instructions, used percentage concentration is mass percent concentration in following examples.
Embodiment 1:
A kind of preparation method of potassium cinnamate, its concrete steps are:
(1), take by weighing 138.8g (1.286mol) silver, 91.18g palladium (0.857mol), be added dropwise to excessive concentration and be 96% nitric acid 400g, be warming up to 90 ℃ after dropwising, stirred 2 hours, filter, in filtrate, add the carbon dust of 265g (22.08mol), simultaneously Dropwise 5 0%KOH solution, vigorous stirring, until system pH=10, continue to stir 1 hour, the carrier carbon dust is fully adsorbed, filter, the gained filter cake is silver suboxide, palladium hydroxide and toner mixture.
(2), will in silver suboxide, palladium hydroxide and toner mixture, add 50% KOH pure water solution 400mL, be cooled to 20 or 24 or 27 or 30 ℃, remain on 20 or 23 or 26 or-30 ℃ and drip formalin 185g (2.284mol), dropwise the back and continue reaction 0.5 hour, then reaction product is filtered, be washed till neutrality with 1200g pure water (it is inferior to give a baby a bath on the third day after its birth, each 400g), oven dry promptly obtains black powder shape solid silver/palladium/carbon catalyst 456.5g.
(3), 28gKOH is dissolved in the 700g deionized water, be mixed with the potassium hydroxide solution of 4wt%, to wherein adding 7g silver/palladium/carbon catalyst, it is even to be stirred to mixing of materials then; Material is warming up to 60 ℃, feed purity oxygen, logical oxygen flow speed is 6L/min, kept logical oxygen 15 minutes, regulating material temperature then is 60 ℃, adds the 140g phenylacrolein under the condition that keeps above-mentioned logical oxygen flow speed, and the dropping time is 5 hours, dropwise the back and continue logical oxygen reaction 10 minutes, get the potassium cinnamate aqueous solution;
(4), will react the potassium cinnamate aqueous solution that generates filters, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle to be used, gained filtrate with KOH adjust pH to 9.5, is cooled to 12 ℃, crystallization, centrifuge dripping, vacuum-drying gets white flakey crystal potassium cinnamate finished product 182.7g, purity 〉=98.5%, yield 92.6% (in phenylacrolein).
Embodiment 2:
(1), take by weighing 127.7g (1.182mol) silver powder, 124.4g (1.168mol) palladium powder, be added dropwise to excessive concentration and be 98% nitric acid 430g, be warming up to 95 ℃ after dropwising, stirred 2 hours, filter, in filtrate, add the carbon dust of 235g (19.58mol), simultaneously Dropwise 5 0%KOH solution, vigorous stirring, until system pH=11, continue to stir 1 hour, the carrier carbon dust is fully adsorbed, filter, the gained filter cake is silver suboxide, palladium hydroxide and toner mixture.
(2), will be in silver suboxide, palladium hydroxide and toner mixture the KOH pure water solution 450mL of Dropwise 5 0%, lower the temperature 25 ℃, remain on 20 or 23 or 26 or-30 ℃ and drip formaldehyde 150g, dropwise the back and continue reaction 1 hour, then reaction product is filtered, filter cake is washed till neutrality with pure water, and oven dry promptly obtains black powder shape solid silver/palladium/carbon catalyst 425.8g.
(3), 33gKOH is dissolved in the 750g deionized water, be mixed with the potassium hydroxide solution of 4.2wt%, to wherein adding 7g silver/palladium/carbon catalyst, it is even to be stirred to mixing of materials then; Material is warming up to 70 ℃, feeds purity oxygen, logical oxygen flow speed is 5L/min, keep logical oxygen 30 minutes, and kept temperature of charge and logical oxygen speed, add the 117g phenylacrolein then, 3.5 hour drip off, dropwise the back and continue logical oxygen reaction 13 minutes, the potassium cinnamate aqueous solution;
(4), will react the potassium cinnamate aqueous solution that generates and filter, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle use, gained filtrate with KOH adjust pH to 10, is cooled to 15 ℃, crystallization, centrifuge dripping, vacuum-drying get finished product 155.5g.By the method identical product is characterized, confirm that this product is a potassium cinnamate, purity 〉=98.5%, yield 94.3% (in phenylacrolein) with embodiment 1.
Embodiment 3:
(1), 40gKOH is dissolved in the 800g deionized water, be mixed with the potassium hydroxide solution of 4.8wt%, the silver/palladium/carbon catalyst of preparation in wherein adding 7g embodiment 1 then, it is even to be stirred to mixing of materials; Material is warming up to 65 ℃, feeds purity oxygen, logical oxygen flow speed is 7L/min, keeps logical oxygen 18 minutes, and the maintenance temperature of charge is added dropwise to the 100g phenylacrolein then, dropwises the back and continues logical oxygen reaction 14 minutes, gets the potassium cinnamate aqueous solution;
(2), will react the potassium cinnamate aqueous solution that generates and filter, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle use, gained filtrate with KOH adjust pH to 10, is cooled to 15 ℃, crystallization, centrifuge dripping, vacuum-drying get finished product 135.1g.By the method identical product is characterized, confirm that this product is a potassium cinnamate, purity 〉=98.5%, yield 95.9% (in phenylacrolein) with embodiment 1.
Embodiment 4:
(1), 50gKOH is dissolved in the 840g deionized water, be mixed with the potassium hydroxide solution of 5.6wt%, the silver/palladium/carbon catalyst of preparation in wherein adding 7g embodiment 2 then, it is even to be stirred to mixing of materials; Material is warming up to 70 ℃, feeds purity oxygen, logical oxygen flow speed is 8L/min, keeps logical oxygen 20 minutes, and the maintenance temperature of charge adds the 70g phenylacrolein then, drips off in 3 hours, dropwises the back and continues logical oxygen reaction 11 minutes, gets the potassium cinnamate aqueous solution;
(2), will react the potassium cinnamate aqueous solution that generates and filter, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle use, gained filtrate with KOH adjust pH to 9.5, is cooled to 15 ℃, crystallization, centrifuge dripping, vacuum-drying get finished product 94.30g.By the method identical product is characterized, confirm that this product is a potassium cinnamate, purity 〉=98.5%, yield 95.6% (in phenylacrolein) with embodiment 1.
Claims (1)
1. the preparation method of a potassium cinnamate the steps include:
A, with silver, palladium by 3: the mixed in molar ratio of 2-3, adding concentration is the nitric acid of 96-98%, is warming up to 90～95 ℃ after dropwising, and stirs 2-3 hour, after silver, palladium are dissolved fully, filter, in filtrate by silver, palladium, carbon dust mol ratio 3: 2-3: 40-50 adds carbon dust, is 10～12 with KOH regulator solution pH value, continue to stir 55-65 minute, the carrier carbon dust is fully adsorbed, filter, the gained filter cake is silver suboxide, palladium hydroxide and toner mixture;
B, the mixture that step (1) is obtained, press mixture, 50% mass percent KOH aqueous solution mol ratio 1: 4-5 is in silver suboxide, palladium hydroxide and toner mixture, add the KOH aqueous solution of 50% mass percent, be cooled to 20-30 ℃, remain on 20-30 ℃ and drip formalin, mixture and formaldehyde mole ratio 1: 1-3, dropwise the back and continue reaction 0.5～1 hour,, be washed to neutrality material filtering, oven dry obtains silver/palladium/carbon catalyst then;
C, add silver/palladium/carbon catalyst in the potassium hydroxide solution of 4～6wt%, the mass ratio of water is 1: 100～120 in silver/palladium/carbon catalyst and the potassium hydroxide solution, and it is even to be stirred to mixing of materials; Material is warming up to 60～70 ℃, feed purity oxygen, logical oxygen flow speed control is built in 5～8L/min, kept logical oxygen 15～30 minutes, regulating material temperature then is 60～75 ℃, adds phenylacrolein under the condition that keeps above-mentioned logical oxygen flow speed, the mass ratio of phenylacrolein and catalyzer is 1: 0.05～0.1, the dropping time is 3-5 hour, dropwises the back and continues logical oxygen reaction 10～15 minutes, gets the potassium cinnamate aqueous solution;
D, the potassium cinnamate aqueous solution is filtered, the gained filter cake is silver/palladium/carbon catalyst, this catalyzer is turned back to the reactor internal recycle use, gained filtrate is cooled to 10～15 ℃, crystallization with KOH adjust pH to 9～10, centrifuge dripping, vacuum-drying get the potassium cinnamate finished product.
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| CN 201010190471 CN101857541B (en) | 2010-05-28 | 2010-05-28 | Method for preparing potassium cinnamate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107397966A (en) * | 2017-09-22 | 2017-11-28 | 徐州益康环保科技有限公司 | A kind of multipurpose high-efficiency environment-friendly deodorant agent |
| CN112939767A (en) * | 2021-01-28 | 2021-06-11 | 武汉能迈科实业有限公司 | Preparation method of potassium cinnamate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919822A (en) * | 2006-07-13 | 2007-02-28 | 武汉远城科技发展有限公司 | Novel method of synthesizing cinnamic acid by catalyzed oxidation cinnamic aldehyde |
| CN101270041A (en) * | 2008-04-30 | 2008-09-24 | 武汉市合中生化制造有限公司 | Catalytic oxidation method of preparing a-methyl cinnamic acid |
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- 2010-05-28 CN CN 201010190471 patent/CN101857541B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919822A (en) * | 2006-07-13 | 2007-02-28 | 武汉远城科技发展有限公司 | Novel method of synthesizing cinnamic acid by catalyzed oxidation cinnamic aldehyde |
| CN101270041A (en) * | 2008-04-30 | 2008-09-24 | 武汉市合中生化制造有限公司 | Catalytic oxidation method of preparing a-methyl cinnamic acid |
Non-Patent Citations (1)
| Title |
|---|
| 《精细化工中间体》 20010430 罗晓燕等 空气氧化法制备肉桂酸 第23-24页 1 第31卷, 第2期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107397966A (en) * | 2017-09-22 | 2017-11-28 | 徐州益康环保科技有限公司 | A kind of multipurpose high-efficiency environment-friendly deodorant agent |
| CN112939767A (en) * | 2021-01-28 | 2021-06-11 | 武汉能迈科实业有限公司 | Preparation method of potassium cinnamate |
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