CN1927803A - Method of preparing calcium propionate and calcium lactate with oyster shell as calcium source - Google Patents
Method of preparing calcium propionate and calcium lactate with oyster shell as calcium source Download PDFInfo
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- CN1927803A CN1927803A CN 200610104562 CN200610104562A CN1927803A CN 1927803 A CN1927803 A CN 1927803A CN 200610104562 CN200610104562 CN 200610104562 CN 200610104562 A CN200610104562 A CN 200610104562A CN 1927803 A CN1927803 A CN 1927803A
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Abstract
The present invention relates to chemical technology, and is especially process of preparing calcium propionate and calcium lactate with oyster shell as calcium source. Oyster shell after being washed, stoved and crushed is made to react chemically with propionic acid and lactic acid to produce calcium propionate and calcium lactate. The preparation process has chemical reaction at 20-60 deg.c for 2-4.5 hr without high temperature calcining and without adding other chemical matter, and has no destroy to amino acid, unsaturated fatty acid, inorganic matter, trace elements and other beneficial matter. The present invention can eliminate environmental pollution caused by oyster shell and has no secondary pollution.
Description
Affiliated technical field:
The present invention relates to chemical treatment and chemical production technical field.Be specifically related to a kind of oyster shells that utilizes and make the method that the calcium source prepares calcium propionate, calcium lactate.
Technical background:
Oyster is with its delicious flavour, nutritious and liked by the human consumer, but people are when edible oyster or processing shellfish, produced a large amount of oyster shellss, and this waste every year is up to millions of tons, if do not made full use of, not only can cause serious pollution, and be a kind of serious wasting of resources environment.It is about 95% to contain lime carbonate in the oyster shells, is a kind of natural, calcium source that organism produces.The japanese food expert develops natural calcium agent oyster shells and does the Food preservation agent, it is that oyster shells is ground, and makes 320 order calcium agent after the energising heat treated, can be used to improve shelf life storage such as vegetables, meat, can obviously reduce the number of bacteria in the food and suppress bacterial reproduction, can also mildew-resistant.As vegetables such as cucumber being immersed 0.3% calcium suspension liquid 15min, meat immerses 1h in the 1% calcium suspension liquid, and its antibacterial effect is better than clorox physiological saline.Food such as meat stuffing can directly add calcium preparation, not only improve preservation period, also can improve sense of food, and can play certain calcium supplementing effect.Oyster shells is a kind of important Chinese medicinal materials, and its extract can suppress influenza virus, bone marrow poliomyelitis virus, also has the effect of antiviral, antibacterium, raising body immunity.In addition, oyster shells also contains and enriches amino acid, unsaturated fatty acids, inanimate matter and trace element etc., and they play important regulatory role in the human physiological activity.
Calcium is the necessary a kind of inanimate matter nutrient substances of people, is to occupy in the human body the 5th formation element behind C, H, N, O.It plays an important role to physiological functions such as nerve conduction, heartbeat adjusting, Muscle contraction, blood coagulation, enzyme activation, endocrine regulation in human body.The shortage of calcium can cause all obstacles in human body, as dysosteogenesis, and poor growth, neuroticism, skeleton bulking etc.Along with the raising of people's living standard and the enhancing of health care consciousness, calcium deficiency and the problem of replenishing the calcium more and more receive the concern of the whole society.Facts have proved, be difficult to absorb enough calcium amounts of needed by human body in people's diet, therefore must replenish calcium preparation and just can reach resident's dietary calcium of Chinese Soclety of Nutrition's recommendation in 2000 with reference to intake.
Calcium preparation is medicine, food homologous preparation.As medicine, can treat the various diseases that causes because of calcium deficiency, evident in efficacy; As protective foods, aspect the various calcium deficiency diseases generations of prevention, assurance HUMAN HEALTH, good effect is arranged also.In China, over more than 20 year, have number to take calcium preparation, and the consumption of annual calcium preparation all have increase by a relatively large margin with hundreds of millions people.According to statistics, from 1980 to 2000 20 in the period of, the calcium preparation of putting on market through the approval of national drug, food sanitation department amounts to kind more than 500, kind surplus wherein the medicine calcium preparation has 300, kind surplus health care calcium food has 200.Formulation has totally 15 kinds more than of tablet, lozenge, chewable tablet, effervescent tablet, film coated tablet, oral liquid, injection liquid, capsule, soft capsule, electuary, powder, pulvis, syrup, dry syrup and beverages etc.
Calcium propionate is as a kind of new food additive that grew up in recent years, and is main as sanitas in foodstuffs industry, can prolong the food fresh keeping phase.Calcium propionate at starch, contain in protein and the grease material mould, good gas gemma produces bacterium, Gram-negative bacteria, flavacin etc. that special efficacy is arranged.Its toxicity is extremely low simultaneously, in mildew-resistant, can produce flavacin.Therefore, calcium propionate is widely used as food, feed anticorrosion, anti-mould fresh keeping agent, its toxicity is far below present widely used Sodium Benzoate, the normal composition that is considered to food, it also is human body metabolism's intermediate product, according to the Food and Argriculture OrganizationFAO and the World Health Organization (FAO/WHO), calcium propionate is the same with other lipid acid can be by the metabolism utilization that is absorbed by the body, supply with the calcium of needed by human, calcium propionate is nontoxic to human body, have no side effect, advocating the modern society of whole food, this is again a tempting part undoubtedly.Particularly along with growth in the living standard, people more and more favor high-quality fresh-keeping foodstuff.
The calcium lactate purposes is also extremely extensive, at the calsium supplement of pharmaceutical industries as humans and animals, participates in the formation of bone and building again of fracture back osseous tissue as medicine, participates in Muscle contraction, neurotransmission, glandular secretion, vision physiological and clotting mechanism etc.; Be used for toothpaste at light industry as scale remover; In foodstuffs industry, calcium lactate is a kind of safe foodstuff additive, stablizer and thickening material etc.; Calcium lactate also is considered to have the fodder additives that potential market is worth most, and is used for aquaculture.
Producing calcium propionate, the common method of calcium lactate and be with calcium mineral matter such as Wingdale, marble, optical calcite, calcites is raw material, will make lime carbonate be converted into calcium oxide after its high-temperature calcination, and calcium oxide is converted into calcium hydroxide again.Calcium oxide or calcium hydroxide and propionic acid, lactic acid reaction generate calcium propionate and calcium lactate.This method has two big shortcomings: (1) energy consumption height, the cost height can cause secondary pollution.(2) contain trace in the natural crystal inevitably to a small amount of heavy metal (as lead, arsenic etc.) and so on harmful element, these harmful elements also are soluble in propionic acid, lactic acid and enter in the product with calcium ion, take calcium nutritious prod or the foodstuff additive that these are feedstock production with the natural crystal for a long time and will produce very bad influence to human body.Therefore, study a kind of energy of both having saved, reduce cost again, environmental again, and do not contain the calcium nutritious prod of harmful heavy metal ion or the production method of foodstuff additive, become the task of top priority of calcium preparation industry.
Summary of the invention:
The present invention relates to chemical treatment and chemical production technical field, be specifically related to a kind of oyster shells that utilizes and make the method that the calcium source prepares calcium propionate, calcium lactate.
The objective of the invention is to provide suitable and make the calcium propionate of new food additive and sanitas, the suitable calcium lactate of making the calcium-supplementing nutritive product, and take for a long time also and can not produce any dysgenic product and production method thereof human body.The present invention will solve in the production of existing calcium propionate, calcium lactate, and energy consumption is big, and the cost height can cause secondary pollution problem.The invention provides a kind of oyster shells that utilizes and make the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that this method comprises the following steps:
(1) oyster shells is pulverized:
Oyster shells is cleaned, dried, and being crushed to fineness is 50 μ m～150 μ m.
(2) chemical reaction:
Oyster shell powder is added in the reaction vessel, and be 8～16 by water with oyster shell powder total mass number ratio: 1 adds entry.20 ℃～60 ℃ and stir under, add concentration in batches and be 5%～25% propionic acid (or lactic acid) solution in wherein, propionic acid (or lactic acid) is 1.2～1.6: 1 with the oyster shell powder mass ratio.Reaction 1.5h～3h is 7.5～9.5 with the pH of alkaline matter conditioned reaction system, continues to react 0.5h～1.5h.
(3) residue aftertreatment:
With reacted material filtering, filter residue is as the raw material reaction that feeds intake again.
(4) filtrate aftertreatment:
Filtrate filtered obtains calcium propionate and calcium lactate after concentrated, filtration, drying.
With comparing with class methods of prior art, advantage of the present invention is:
1. utilization of waste material, minimizing are polluted
Present domestic oyster shells waste if do not made full use of, can cause severe contamination up to millions of tons to environment every year.Utilize discarded Activated Ca made by oyster shell lime carbonate, calcium lactate, can turn waste into wealth.
2. environmental protection
Filter a small amount of oyster shells waste residue that obtains in the production, feeding intake as raw material once more recycles; The water of condensation that concentrate to produce is used for the neutralization reaction water, and whole production is not discharged waste residue and deleterious waste water, waste gas.Therefore the environmental pollution that had both solved oyster shells and caused does not produce secondary environmental pollution again.
3. production technique is simple
Do the calcium source according to the present invention with oyster shells and prepare calcium propionate, calcium lactate, production technique is simple, and whole process of production does not relate to problems such as high-temperature, high pressure, condition of high vacuum degree, highly corrosive, high-leveled and difficult technology control, and investment of production equipment is little.
4. production cost is low
The depleted oyster shells is as the calcium source, and the raw material acquisition expenses is low; Oyster shells is without crossing high-temperature calcination, and energy consumption is low; Production unit is simple, and facility investment is low; The whole process of production cycle is short.So production cost is low.
5. product calcium propionate, calcium lactate excellent performance
Oyster shells is without crossing high-temperature calcination, and amino acid wherein, unsaturated fatty acids, inanimate matter and trace element etc. are not destroyed to human body beneficial's material, and product calcium propionate, calcium lactate are preferably as foodstuff additive, sanitas or calcium nutritious prod.The product calcium propionate meets food grade preservative calcium propionate GB6225-86 national standard, and the product calcium lactate also meets the GB6226-86 national standard.
Embodiment 1:
Oyster shells is cleaned, dried, be crushed to fineness less than 74 μ m (crossing 200 eye mesh screens).
200 order oyster shell powder 50g and 200mL water are added in the 2000mL there-necked flask, under 35 ℃ and mechanical stirring (stirring velocity is about 120r/min), add concentration in batches and be 10% propionic acid solution 670mL, stirring reaction 2.5h is with Ca (OH)
2Conditioned reaction system pH is about 9.0, continues reaction 1h.
With reacted material decompress filter, weigh after the filter residue and drying, as the raw material reaction that feeds intake again.Filtrate is concentrated near doing, and crystal obtains product calcium propionate 73g at 80 ℃～85 ℃ oven dry 4h, and productive rate is 95%.
Embodiment 2
Oyster shells is scrubbed clean, dries, be crushed to fineness less than 154 μ m (crossing 100 eye mesh screens).
Propionic acid solution 720g with 17% adds in the 1000mL there-necked flask, under 20 ℃ and mechanical stirring (stirring velocity is about 140r/min), constantly adding fineness is 100 purpose oyster shell powder 100g, stirring reaction 1.5h, pH with CaO conditioned reaction system is about 8.0, continues reaction 1.5h.
With reacted material decompress filter, weigh after the filter residue and drying, as the raw material reaction that feeds intake again.Filtrate is concentrated near doing, and crystal obtains product calcium propionate 141g at 100 ℃～105 ℃ oven dry 2h, and productive rate is 95%.
Embodiment 3
Oyster shells is scrubbed clean, dries, be crushed to fineness less than 100 μ m.
Oyster shell powder 60kg and 260L are added in the stainless steel cauldron of 2000L, under 50 ℃ and mechanical stirring, add concentration in batches and be 9% propionic acid solution 800L, stirring reaction 2.5h is with Ca (OH)
2The pH of conditioned reaction system is about 8.0, continues reaction 1.5h.
With reacted material filtration under diminished pressure, filter residue is as the raw material reaction that feeds intake again.Filtrate decompression is concentrated into 20% (w/w), and the solution that obtains carries out spraying drying (spraying drying condition: feeding concentration 20%, flow 30L/h, 200 ℃ of temperature ins, 80 ℃ of temperature outs), obtains white calcium propionate powder 85kg, and finished product packing is the 25kg/ bag.
Embodiment 4:
Oyster shells is scrubbed clean, dries, be crushed to fineness less than 74 μ m (crossing 200 eye mesh screens).
50g oyster shell powder and 300mL water are added in the 2000mL there-necked flask, under 30 ℃ and mechanical stirring (stirring velocity is 120r/min), add concentration in batches and be 15% lactic acid solution 600mL, stirring reaction 2.5h is with Ca (OH)
2The pH of conditioned reaction system is about 8.5, continues reaction 1h.
With reacted material filtration under diminished pressure, weigh after the filter residue and drying, as the raw material reaction that feeds intake again.Filtrate is concentrated into 500mL, leaves standstill crystallization, filters, and crystal gets calcium lactate 98g at 80 ℃～85 ℃ oven dry 4h, and productive rate is 92%.
Embodiment 5:
Oyster shells is scrubbed clean, dries, be crushed to fineness less than 102 μ m (crossing 150 eye mesh screens).
Lactic acid solution 280g with 12% adds in the 500mL there-necked flask, under 20 ℃ and mechanical stirring (stirring velocity is about 140r/min), constantly adding fineness is 100 purpose oyster shell powder 20g, stirring reaction 1.5h, pH with CaO conditioned reaction system is about 8.0, continues reaction 1.5h.
Filtrate is concentrated into 200mL, leaves standstill crystallization, filters, and dries 3h down at 90 ℃～95 ℃, gets calcium lactate 33.5g, and productive rate is 94%.
Embodiment 6:.
Oyster shells is scrubbed clean, dries, be crushed to the little 154 μ m of fineness.
12% lactic acid solution 1.5t is added in the 2000L stainless steel cauldron, 50 ℃ and stir under (stirring velocity is 120r/min), constantly adding fineness is 100 purpose oyster shell powder 100kg, stirring reaction 2.5h is with Ca (OH)
2The pH of conditioned reaction system is about about 8.5, continues reaction 1h.
With reacted material filtering, filter residue is as the raw material reaction that feeds intake again.Filtrate is concentrated into 1000L, leaves standstill crystallization, filters, and 95 ℃～100 ℃ oven dry down, obtains calcium lactate 180kg, productive rate 95%.
Claims (11)
1. one kind is utilized oyster shells to make the method that the calcium source prepares calcium propionate, calcium lactate, and this method comprises the following steps:
(1) oyster shells is pulverized
Oyster shells is cleaned, dried, and being crushed to fineness is 50 μ m～150 μ m.
(2) chemical reaction
Oyster shell powder is added in the reaction vessel, and be 8～16 by water and oyster shell powder ratio of quality and the number of copies: 1 adds entry.Under 20 ℃～60 ℃ and mechanical stirring, add concentration in batches and be 5%～25% propionic acid or lactic acid solution in wherein, propionic acid or lactic acid and oyster shell powder ratio of quality and the number of copies are 1.2～1.6: 1.Reaction 1.5h～3h is 7.5～9.5 with the pH of alkaline matter conditioned reaction system, continues to react 0.5h～1.5h.
(3) residue aftertreatment
With reacted material filtering, filter residue is as the part material reaction that feeds intake again.
(4) filtrate aftertreatment
Filtrate filtered is concentrated into and a large amount of crystal occur, is thick product.
(5) product drying
Thick product after filtration, obtain calcium propionate or calcium lactate after the drying.
2. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (1), the fineness of oyster shell powder is 50 μ m～150 μ m.
3. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), water and oyster shell powder mass ratio are 8～16: 1.
4. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), propionic acid or concentration of lactic acid are 5%～25%.
5. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), pure propionic acid or lactic acid and oyster shell powder ratio of quality and the number of copies are 1.2～1.6: 1.
6. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), chemical reaction temperature is 20 ℃～60 ℃.
7. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), stirring velocity is 120r/min～150r/min.
8. a kind of oyster shell powder that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), the reaction times is 1.5h～3h.
9. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), alkaline matter is Ca (OH)
2Or CaO.
10. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), the pH of reaction system is 7.5～9.5.
11. a kind of oyster shells that utilizes described in claim 1 is made the method that the calcium source prepares calcium propionate, calcium lactate, it is characterized in that: in the described step (2), it is 0.5h～1.5h that the reaction times is continued in the pH value of regulation system back.
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| CNB2006101045626A CN100551893C (en) | 2006-09-13 | 2006-09-13 | A kind of oyster shells that utilizes is made the method that the calcium source prepares calcium propionate, calcium lactate |
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| CN1927803A true CN1927803A (en) | 2007-03-14 |
| CN100551893C CN100551893C (en) | 2009-10-21 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440031B (en) * | 2008-11-26 | 2011-07-20 | 青岛大学 | Method for preparing high-purity calcium lactate from oyster shell |
| CN101747174B (en) * | 2010-01-15 | 2013-04-17 | 连云港树人科创食品添加剂有限公司 | Preparation method of calcium propionate and second-effect flash distillation plant |
| CN103848408A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院海洋研究所 | Method for preparing calcium hydrogen phosphate by using shells |
| CN107974238A (en) * | 2017-12-18 | 2018-05-01 | 雷笑天 | A kind of preparation method of low-corrosiveness deicing salt |
| CN108217708A (en) * | 2017-12-20 | 2018-06-29 | 五邑大学 | A kind of methods and applications that nano biological calcium carbonate is prepared using waste shell as raw material |
| 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 |
| CN114349566A (en) * | 2021-12-30 | 2022-04-15 | 江西科农沃科技有限责任公司 | Calcium fertilizer and preparation method thereof |
-
2006
- 2006-09-13 CN CNB2006101045626A patent/CN100551893C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440031B (en) * | 2008-11-26 | 2011-07-20 | 青岛大学 | Method for preparing high-purity calcium lactate from oyster shell |
| CN101747174B (en) * | 2010-01-15 | 2013-04-17 | 连云港树人科创食品添加剂有限公司 | Preparation method of calcium propionate and second-effect flash distillation plant |
| CN103848408A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院海洋研究所 | Method for preparing calcium hydrogen phosphate by using shells |
| CN103848408B (en) * | 2012-11-28 | 2016-04-13 | 中国科学院海洋研究所 | A kind of method utilizing shell to prepare secondary calcium phosphate |
| CN107974238A (en) * | 2017-12-18 | 2018-05-01 | 雷笑天 | A kind of preparation method of low-corrosiveness deicing salt |
| CN108217708A (en) * | 2017-12-20 | 2018-06-29 | 五邑大学 | A kind of methods and applications that nano biological calcium carbonate is prepared using waste shell as raw material |
| 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 |
| CN114349566A (en) * | 2021-12-30 | 2022-04-15 | 江西科农沃科技有限责任公司 | Calcium fertilizer and preparation method thereof |
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| CN100551893C (en) | 2009-10-21 |
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