CN102675082A - Preparation method of calcium propionate by egg shell - Google Patents
Preparation method of calcium propionate by egg shell Download PDFInfo
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- CN102675082A CN102675082A CN2012101282203A CN201210128220A CN102675082A CN 102675082 A CN102675082 A CN 102675082A CN 2012101282203 A CN2012101282203 A CN 2012101282203A CN 201210128220 A CN201210128220 A CN 201210128220A CN 102675082 A CN102675082 A CN 102675082A
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Abstract
The invention discloses a preparation method of calcium propionate by egg shell. The preparation method of calcium propionate by egg shell includes egg shell pretreatment, shell membrane separation, neutralization reaction, purification reaction, filtration, pH adjustment, concentration, drying and the like. Shell membrane separation is performed under physical mixing by adding water. Based on a direct neutralization method, secondary neutralization reaction method using egg shell powder to prepare calcium propionate is established. Sodium carboxymethylcellulose is used as flocculant for purification. Therefore, the prior art problems that egg membrane separation is poor in effect, neutralization reaction is incomplete, utilization rate of propionic acid is low, product quality is instable and the like are solved.
Description
Technical field
The present invention relates to the preparation method of calcium propionate, be specifically related to a kind of method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate.
Background technology
China's annual generation eggshell about about 4,000,000 tons, only is used for the Creta Preparata of fertilizer and feed greatly on a small quantity, and other is all thrown away as waste, causes ample resources waste and environmental pollution.Mainly contain CaCO in the Ovum crusta Gallus domesticus
3, other has a spot of MgCO
3, Ca
3(PO4)
2, Mg
3(PO
4)
2And protein, heavy metal content is low, contains 70% protein and few part lipid in the egg shell membrane, can be used for fields such as medicine, makeup and material.
Calcium propionate belongs to acid mould inhibitor; To human non-toxic, have no side effect, and also have to suppress produce the effect of flavacin, and have must detoxification; Can be widely used in the mildew-resistant of food such as bread, cake, calcium propionate also can be used as fodder additives, preservation agent, auxiliary pharmaceutical adjuvant in addition.
The method of utilizing eggshell to prepare calcium propionate has high-temperature calcination and direct neutralisation.High-temperature calcination is that eggshell is at high temperature calcined, and the lime carbonate decomposition is CaO in the eggshell, and adding zero(ppm) water is mixed with certain density milk of lime, adds the propionic acid reaction then, and last warp filters, evaporates, concentrates and drying obtains the calcium propionate finished product.Directly neutralisation is with eggshell and propionic acid reaction, obtains calcium propionate solution after the purified filtration, obtains the calcium propionate finished product through concentrate drying again.The productive rate and the content of the calcium propionate that the available technology adopting high-temperature calcination prepares are higher, but need calcine eggshell, and power consumption is big, and cost is high, and a large amount of carbonic acid gas and the dust of calcining generation, cause environmental pollution.
Though the influence that existing direct neutralisation has avoided calcining that environment is caused, exist following problem: shell membrane separation method efficient is not high, and isolating egg shell membrane is easily collecting not; Neutralization reaction is not thorough; The propionic acid utilization ratio is low; Only add alkaline matter after the reaction and carry out purifying, it is not thorough to remove mg ion, and product quality is unstable.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate, belong to direct neutralisation, this method has solved that prior art mesochite membrane sepn efficient is low, neutralization reaction not thoroughly, the propionic acid utilization ratio is low and a difficult problem such as product quality instability.
Above-mentioned purpose realizes through following technical scheme:
A kind of method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate comprises the steps:
(1) eggshell pre-treatment:
Ovum crusta Gallus domesticus is centrifugal, go to clean behind the residual egg white, drying, crushing screening, egg-shell meal is subsequent use, and thick eggshell carries out shell membrane to be separated;
(2) shell membrane separates:
In whisking appliance, add the thick eggshell of 1 weight part and the water of 6-12 weight part, stirred 10-30 minute, leave standstill with 300-600 rev/min speed; Obtain bottom egg-shell meal and upper strata egg shell membrane liquid; Filter, obtain egg shell membrane after the filtrating drying, the egg-shell meal in filter residue and the step (1) merges;
(3) neutralization reaction:
The egg-shell meal of input 1 weight part and the water of 8-15 weight part in reaction kettle, stirring back added the propionic acid of 1.6-2.4 weight part altogether at twice in 30 minutes, after reacting 1.5-3 hour under 50-80 ℃; Left standstill 5 minutes; Get the supernatant concentrating under reduced pressure and get calcium propionate solution, reclaim the propionic acid that evaporates simultaneously, the propionic acid of recovery gets into reaction kettle and egg-shell meal carries out the secondary neutralization reaction; Reaction times is 50-100 minute, filters to obtain calcium propionate solution;
(4) purification reaction:
Adding mass percent in the calcium propionate solution that after neutralization reaction and secondary neutralization reaction, obtains is the calcium hydroxide of 1-1.8%; Reaction is 15-20 minute under 60-90 ℃ of condition; Add the Xylo-Mucine that mass percent is 0.002-0.005% then; Stirred 1 minute earlier fast, stir 3 minutes at a slow speed again after, left standstill 5 minutes;
(5) filter:
With the material filtering behind the purification reaction, collect filtrating;
(6) regulate pH value, concentrated, dry:
To filtrate and use third acid for adjusting pH value is 7.5, is concentrated into then and separates out the calcium propionate crystallization, the dry calcium propionate that gets.
The invention has the beneficial effects as follows:
(1) the present invention has set up a kind of new shell membrane separation method, through screening, the egg-shell meal that only contains a small amount of egg shell membrane directly is used for neutralization reaction, has reduced the isolating treatment capacity of shell membrane.Thick eggshell adopts the physics mode that adds the water stirring to carry out the shell membrane separation, and cost is low, and is pollution-free, good separating effect, and the egg-shell meal recovery can reach 95.6%, and the residual rate of egg shell membrane is merely 0.38% in the egg-shell meal.Compare with other method, it is about 40% that this method reduces shell membrane separating treatment amount, and it is about 1.47% that the recovery of egg-shell meal has improved, and the egg shell membrane residual quantity has reduced about 36% in the egg-shell meal.This treating processes is gentle, and little to the egg shell membrane influence, the egg shell membrane that obtains can be applicable to fields such as medicine, makeup and material, has made full use of eggshell resource.
(2) set up secondary neutralization reaction method; Unreacted propionic acid after neutralization reaction is recycled; The propionic acid that reclaims carries out the secondary neutralization reaction with residual egg-shell meal once more; Improved the propionic acid utilization ratio, compared, obtained unit calcium propionate consumption propionic acid amount and reduced about 15% with existing method.
(3) use Xylo-Mucine to carry out purification process as flocculation agent first, flocculation agent can increase the particle agglomeration particle diameter, promotes Mg (OH)
2Crystalline forms and deposition, reduces the time of purifying, has improved the stability of product quality.
(4) help environmental protection and comprehensive utilization of resources: contain residual egg white in the eggshell, will mosquitos and flies in heaps, stench is unpleasant if untimely cleaning or utilization, form serious environmental and pollute.And the present invention utilizes discarded Ovum crusta Gallus domesticus to prepare calcium propionate, turns waste into wealth, and improves the comprehensive utilization of resources rate.The whole process of preparation method of the present invention is in the state of semitight, except that producing carbonic acid gas, does not produce other waste gas, does not produce solid refuse, and whole process of production does not pollute the environment.
(5) with short production cycle, production unit requires lower, and energy consumption and production cost are low.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
A kind of method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate comprises the steps:
(1) eggshell pre-treatment:
Ovum crusta Gallus domesticus is centrifugal, to go to clean behind the residual egg white, drying is got the pulverizing of 100Kg Ovum crusta Gallus domesticus and is sieved, and gets egg-shell meal 39kg, directly is used for neutralization reaction, gets thick eggshell 61kg, uses the method in (2) to carry out the shell membrane separation.
(2) shell membrane separates:
To treat that the thick eggshell of isolating 61kg places whisking appliance, and add the water of 732kg, agitator, stirring velocity are 600 rev/mins; Stir after 10 minutes, left standstill 5 minutes, obtain bottom egg-shell meal and upper strata egg shell membrane liquid; Filtering separation obtains egg shell membrane after the filtrating drying, obtains filter residue 55.5kg simultaneously; Egg-shell meal in this part filter residue and the step (1) is merged, amount to 94.5kg, be used for neutralization reaction.
(3) neutralization reaction:
In reaction kettle, add the egg-shell meal of 94.5kg and the water of 1418kg, in 30 minutes, add the propionic acid of 208kg altogether behind the stirring and evenly mixing at twice, after reacting 1.5 hours under 80 ℃; Left standstill 5 minutes, and got supernatant, concentrating under reduced pressure gets neutralization reaction calcium propionate solution one time; Reclaim the propionic acid that evaporates simultaneously; The propionic acid that reclaims gets into reaction kettle and egg-shell meal carries out the secondary neutralization reaction, and the reaction times is 50 minutes, filters to obtain secondary neutralization reaction calcium propionate solution.
(4) purification reaction:
Merge the calcium propionate solution that neutralization reaction and secondary neutralization reaction obtain; The adding mass percent is 1.8% calcium hydroxide; Reaction is 15 minutes under 90 ℃ of conditions, adds mass percent then and be 0.003% Xylo-Mucine, stirs 1 minute fast earlier; After stirring 3 minutes at a slow speed again, left standstill 5 minutes.
(5) filter:
With the material filtering behind the purification reaction, collect filtrating.
(6) regulate pH value, concentrated, dry:
To filtrate and use third acid for adjusting pH value is 7.5, is concentrated into then and separates out a large amount of calcium propionate crystallizations, the dry calcium propionate 173.3kg that gets.
The recovery of egg-shell meal was 94.5% during this embodiment shell membrane separated, and the residual rate of egg shell membrane in egg-shell meal is 0.38%, and the propionic acid utilization ratio is 67.2%.The calcium propionate productive rate is 98.58%, and product purity reaches 99.20%.
Embodiment 2
A kind of method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate comprises the steps:
(1) the eggshell pre-treatment is identical with embodiment 1.
(2) shell membrane separates:
To treat that the thick egg-shell meal of isolating 61kg places whisking appliance, adds the water of 366kg, agitator again; Stirring velocity is 300 rev/mins, stirs after 30 minutes, leaves standstill 5 minutes; Obtain bottom egg-shell meal and upper strata egg shell membrane liquid; Filtering separation obtains egg shell membrane after the filtrating drying, obtains filter residue 56.9kg simultaneously.Egg-shell meal in this part filter residue and the step (1) is merged, amount to 95.9kg, be used for neutralization reaction.
(3) neutralization reaction:
In reaction kettle, add the egg-shell meal of 95.9kg and the water of 768kg, in 30 minutes, add the propionic acid of 173kg altogether behind the stirring and evenly mixing at twice, after reacting 3 hours under 60 ℃; Left standstill 5 minutes, and got supernatant, concentrating under reduced pressure gets neutralization reaction calcium propionate solution one time; Reclaim the propionic acid that evaporates simultaneously; The propionic acid that reclaims gets into reaction kettle and egg-shell meal carries out the secondary neutralization reaction, and the reaction times is 100 minutes, filters to obtain secondary neutralization reaction calcium propionate solution.
(4) purification reaction:
Merge the calcium propionate solution that neutralization reaction and secondary neutralization reaction obtain; The adding mass percent is 1% calcium hydroxide; Reaction is 20 minutes under 60 ℃ of conditions, adds massfraction then and be 0.005% Xylo-Mucine, stirs 1 minute fast earlier; After stirring 3 minutes at a slow speed again, left standstill 5 minutes.
(5) filter: identical with embodiment 1.
(6) regulate pH value, concentrated, dry
To filtrate and use third acid for adjusting pH value is 7.5, is concentrated into then and separates out a large amount of calcium propionate crystallizations, the dry calcium propionate 171.6Kg that gets.
The recovery of egg-shell meal was 95.6% during this embodiment shell membrane separated, and the residual rate of egg shell membrane in egg-shell meal is 0.53%, and the propionic acid utilization ratio is 82.1%.The calcium propionate productive rate is 96.18%, and product purity reaches 99.12%.
Claims (1)
1. a method of utilizing Ovum crusta Gallus domesticus to prepare calcium propionate is characterized in that comprising the steps:
(1) eggshell pre-treatment:
Ovum crusta Gallus domesticus is centrifugal, go to clean behind the residual egg white, drying, crushing screening, egg-shell meal is subsequent use, and thick eggshell carries out shell membrane to be separated;
(2) shell membrane separates:
In whisking appliance, add the thick eggshell of 1 weight part and the water of 6-12 weight part, stirred 10-30 minute, leave standstill with 300-600 rev/min speed; Obtain bottom egg-shell meal and upper strata egg shell membrane liquid; Filter, obtain egg shell membrane after the filtrating drying, the egg-shell meal in filter residue and the step (1) merges;
(3) neutralization reaction:
The egg-shell meal of input 1 weight part and the water of 8-15 weight part in reaction kettle, stirring back added the propionic acid of 1.6-2.4 weight part altogether at twice in 30 minutes, after reacting 1.5-3 hour under 50-80 ℃; Left standstill 5 minutes; Get the supernatant concentrating under reduced pressure and get calcium propionate solution, reclaim the propionic acid that evaporates simultaneously, the propionic acid of recovery gets into reaction kettle and egg-shell meal carries out the secondary neutralization reaction; Reaction times is 50-100 minute, filters to obtain calcium propionate solution;
(4) purification reaction:
Adding mass percent in the calcium propionate solution that after neutralization reaction and secondary neutralization reaction, obtains is the calcium hydroxide of 1-1.8%; Reaction is 15-20 minute under 60-90 ℃ of condition; Add the Xylo-Mucine that mass percent is 0.002-0.005% then; Stirred 1 minute earlier fast, stir 3 minutes at a slow speed again after, left standstill 5 minutes;
(5) filter:
With the material filtering behind the purification reaction, collect filtrating;
(6) regulate pH value, concentrated, dry:
To filtrate and use third acid for adjusting pH value is 7.5, is concentrated into then and separates out the calcium propionate crystallization, the dry calcium propionate that gets.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103302080A (en) * | 2013-06-27 | 2013-09-18 | 北京二商健力食品科技有限公司 | Preparation method of eggshell powder and processing device |
| CN103330237A (en) * | 2013-06-27 | 2013-10-02 | 北京二商健力食品科技有限公司 | Method and device for processing egg shell meal |
| CN103340441A (en) * | 2013-07-01 | 2013-10-09 | 北京二商健力食品科技有限公司 | Poultry egg shell-membrane separation equipment |
| CN109998116A (en) * | 2019-04-19 | 2019-07-12 | 福建农林大学 | A kind of preparation method of enzymatic hydrolysis and fermentation in combining conversion extraction eggshell calcium lactate |
| CN111995514A (en) * | 2019-05-27 | 2020-11-27 | 浙江工业大学 | Method for preparing nano-scale calcium acetate from shells |
| CN112409161A (en) * | 2020-11-23 | 2021-02-26 | 南通奥凯生物技术开发有限公司 | Preparation method of high-purity feed additive calcium propionate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103302080A (en) * | 2013-06-27 | 2013-09-18 | 北京二商健力食品科技有限公司 | Preparation method of eggshell powder and processing device |
| CN103330237A (en) * | 2013-06-27 | 2013-10-02 | 北京二商健力食品科技有限公司 | Method and device for processing egg shell meal |
| CN103330237B (en) * | 2013-06-27 | 2015-08-12 | 北京二商健力食品科技有限公司 | A kind of processing method of egg-shell meal and process equipment |
| CN103302080B (en) * | 2013-06-27 | 2015-12-02 | 北京二商健力食品科技有限公司 | A kind of preparation method of egg-shell meal and process equipment |
| CN103340441A (en) * | 2013-07-01 | 2013-10-09 | 北京二商健力食品科技有限公司 | Poultry egg shell-membrane separation equipment |
| CN109998116A (en) * | 2019-04-19 | 2019-07-12 | 福建农林大学 | A kind of preparation method of enzymatic hydrolysis and fermentation in combining conversion extraction eggshell calcium lactate |
| CN111995514A (en) * | 2019-05-27 | 2020-11-27 | 浙江工业大学 | Method for preparing nano-scale calcium acetate from shells |
| CN111995514B (en) * | 2019-05-27 | 2022-07-08 | 浙江工业大学 | Method for preparing nano-scale calcium acetate from shells |
| CN112409161A (en) * | 2020-11-23 | 2021-02-26 | 南通奥凯生物技术开发有限公司 | Preparation method of high-purity feed additive calcium propionate |
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