CN102626181B - Calcium citrate organic feed additive and preparation method thereof - Google Patents

Abstract

The invention discloses a calcium citrate organic feed additive and a preparation method thereof. Calcium citrate is calcium citrate comprising four crystallization water as a main ingredient. The preparation method of the calcium citrate comprising the four crystallization water comprises the following steps of: (1), putting water in a reaction kettle to be boiled; (2), uniformly feeding citric acid into the reaction kettle, stirring for 3-10 min till completely dissolving, and keeping at 60-90 DEG C; (3), slowly and uniformly feeding light calcium carbonate, and stirring till completely reacting to obtain the calcium citrate ((C6H5O7)2Ca3)4H2O) comprising the four crystallization water; (4), precipitating; (5), dehydrating; (6), drying; (7), screening; and (8), checking and packaging. The calcium citrate ((C6H5O7)2Ca3)4H2O) comprising the four crystallization water is slightly soluble in water and has good dissolving property and high animal absorbance under the slight acid condition.

Description

Calcium citrate organic feed additive and preparation method thereof

Technical field

The present invention relates to a kind of production method of animal organic feed additive, particularly a kind of calcium citrate organic feed additive and preparation method thereof.

Background technology

China's feed industry starts flourish from the beginning of the eighties, the history of existing two more than ten years, has reached 1.78 hundred million tons to China's feed total output in 2011 so far, occupies first, the whole world.The annual production of mixed feed reaches 5119.5 ten thousand tons.But compared with developed countries, China's additive industry also exists some problems in fast-developing, wherein the research and development of new varieties, novel form feed addictive lag behind the market demand far away.With regard to trace mineral supplement, in the production process of two more than ten years, adding in a large number inorganic microelements always, because the reasons in structure of these inorganic microelements own causes its biological value lower, animal absorbs limited in one's ability, therefore need very large addition, and animal real absorbent be only seldom one, general uptake is only below 1/3 of addition, do not have the trace element absorbing from the ight soil of animal, to excrete or be deposited on the bone of animal, liver is even in muscle, thereby caused a large amount of wastings of resources, the problem such as environmental pollution and food security, the health of harm humans.

Along with the development of feed industry and the progress of aquaculture, organic trace element feed addictive has become the indispensable raw material of mixed feed.People are according to different animals nutritional need, in mixed feed, add the feed addictives such as trace element of various dose to carry out balanced nutrients composition, to reach, promote animal to produce, improve product quality, improve food conversion ratio, reduce feeding cost, the object of increasing economic efficiency.

Calcium is the first mineral element in animal body, and calcium accounts for the 1%-2% of the weight of animals.99% of calcium exists in bone and tooth, and remaining calcium is present in soft tissue body fluid.Obviously, calcium the growth of bone and tooth with maintain in play an important role, in addition, calcium also has many important biological functions.Calcium, to secretion of the activity of the contraction of the transmission of blood clotting, nerve impulse, muscle, enzyme and hormone etc., has decisive role.Can there is rickets while lacking calcium in young animal, osteomalacia appears in adults while lacking calcium, and calcium, phosphorus ratio imbalance also can cause acalcicosis, and calcium deficiency, except causing bone disorders, also causes that breeding performonce fo animals declines simultaneously.

On herding is produced, the inorganic calcium classes such as pulverized limestone, calcium carbonate and calcium monohydrogen phosphate of mainly take are main calcium source at present, wherein calcium carbonate because calcium content is high, safe, effective, particularly inexpensive advantage, is used the most extensive.Although calcium carbonate calcium content is high, cheap, because dissolution of calcium carbonate is extremely low, it dissolve to need lower pH, just can be absorbed after must be under one's belt generating ionized calcium with a large amount of acid reaction.Calcium carbonate has acidophilia, in and after hydrochloric acid in gastric juice, produce carbon dioxide and cause animal intestines and stomach flatulence.Calcium carbonate major part has drained with difficulty soluble salt form, or deposition in animal body, causes the waste of raw material, and calcium absorption is bad to be caused calcium phosphorus ration imbalance and causes aphosphorosis.Especially young animal, digestive system development imperfection, stomach is secreted sour ability not as good as adults, and stomach inner pH value, higher than Adult Pig, directly affects its absorption to calcium.Especially early-weaned piglets, ablactation stress causes that stomach inner pH value significantly rises, and is unfavorable for growth.And inorganic calcium easily causes electrolytical imbalance, cause piglet white scour; Calcium carbonate also disturbs the absorption of the inorganic ions such as iron, zinc simultaneously.

(molecular formula is C to calcium citrate ₁₂h ₁₀ca ₃o ₁₄) as a kind of novel calcium preparation, be widely used in medicine and the mankind at home and abroad and replenished the calcium.In U.S. < < clinician handbook on the desk 1993 version (PCR), recommendation calcium citrate is as clinical conventional calcium tonic, and < < U.S. food additive standard > > version (PCC) in 1996 and Japanese < < japanese food additive official compendium > > sixth version in 1992 have also recorded this kind.At Chinese < < Chinese food industrial standard compilation > >, food additives have recorded this product, within 1997, ministry of Health of China approval calcium citrate is health food, within 1998, calcium citrate is approved for national new drug in China, < < Chinese family OTC guide > > in 1999 (in the effect of calcium citrate and purposes have been done to clear and definite explanation.Also there are clearly regulation in World of Food in 1985 and agricultural organization/World Health Organization (FAO/WHO) to the security of calcium citrate, and acceptable daily intake (ADI) is not done particular provisions, does not in fact show toxicity.

With respect to calcium carbonate, the dissolubility of calcium citrate is good, is that 10 times of calcium carbonate (generally believe at present, the calcium source biological value that solubility is larger is higher), so strong to hydrochloric acid in gastric juice dependence unlike calcium carbonate, even in water, can dissolve, little to gastrointestinal irritation, wholesomeness is high.It not only can be used as the calcium supplementing preparation of animal, simultaneously can also be as acidulant necessary in animal body.Therefore, compare with inorganic calcium (as calcium carbonate and calcium monohydrogen phosphate), calcium citrate can significantly improve the biological value of calcium, can directly by animal, be absorbed, and not affect the particularly absorption of iron of other mineral matter; In not understanding and hydrochloric acid in gastric juice produce carbon dioxide, therefore can not cause flatulence and cause the discomfort of animal body.Simultaneously, citric acid is a kind of trophism acidulant, it is the intermediate product of human body energy metabolism, there is important biological function: be the important medium in acetyl-CoA synthctic fat process, it is one of important substance forming in mitochondria respiratory chain, can regulate cAMP active, participate in a series of important reactions such as human body energy, structure and enzyme guarantee, can reduce daily ration and animal alimentary canal pH value, change microbial bacteria group structure in alimentary canal, improve digestive tract enzyme activity, promote the absorption of vitamin, mineral element, improve the digestibility of nutriment.The experimental study that Yang Jun etc. (1999) absorb in rat body with citric acid one malic acid calcium salt, result shows, calcium citrate various dose group feed calcium absorptivity and Retention, all apparently higher than the calcium carbonate group of same dosage, show that the absorption Retention of calcium citrate in rat body is obviously better than calcium carbonate.This explanation calcium citrate is a kind of desirable calcium preparation, has higher biologically active, and supplement calcium, the in the situation that of other allowance of nutrients abundance, as feed calcium source, can guarantee and promote the healthy growth and development of toy with calcium citrate effectively.

Calcium citrate has been widely used in the mankind and has replenished the calcium, citric acid has also been widely used in Production of Livestock and Poultry application as acidulant, therefore, with calcium citrate, substitute traditional calcium carbonate, as the calcium source in livestock and poultry diet, be feasible, for animal particularly stomach secrete the young animal of sour scarce capacity, calcium citrate is by the calcium source that is a kind of more high-quality.

Although but people know, calcium citrate is a kind of good calcium tonic, and does not know that calcium citrate is along with the difference of molecular structure also has difference because calcium citrate has several crystalline solid, 1, ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂o (four crystallizations water); 2, ((C ₆h ₅o ₇) 2Ca ₃) 3H ₂o (three crystallizations water); 3, ((C ₆h ₅o ₇) 2Ca ₃) 2H ₂o (two crystallizations water); 4, ((C ₆h ₅o ₇) 2Ca ₃) H ₂o (crystallization water); 5, ((C ₆h ₅o ₇) 2Ca ₃) (anhydrous), in the calcium citrate of these several crystalline solid, what the most easily by animal, absorbed is the calcium citrate of four crystallizations water, different reactants and reaction condition obtain the citric acid of the different crystallizations water, so the calcium citrate of producing four crystallizations water has become the direction of people's research, in recent years, open source literature has also been reported the production method of some calcium citrates, for example:

1, [autograph] utilizes eggshell to produce Primary Study [author] Bin Dongmei of calcium citrate, Yi Cheng, Ma Meihu, Luo Renzhi, [mechanism] [1] Hunan environmental organism Vocationl Technical College, [2] Agricultural University Of Hunan, [periodical name] modern food science and technology .2006,22 (3) .-6-9,5[digest] for making full use of the CaCO in eggshell ₃, adopt neutralisation to prepare calcium citrate, make inorganic calcium wherein be converted into organic calcium, carried out the affect experimental studies of factor on product yield and purity such as calcination condition, raw material proportioning, reactant concentration, temperature, time.Result shows: optimum process conditions are respectively: eggshell is at 900 ℃ of calcining and decomposing 1-2h, and CaO yield is more than 95%.Neutralization reaction condition: lime milk concentration 5%, citric acid concentration 50%, 60 ℃ of reaction temperatures, reaction time 1h, product yield is high, quality good, safety non-toxic.

2, [autograph] prepares research [author] Lin Liliwen strong Pan Rong pattern stone ripple [mechanism] Zhanjiang Normal University's chemical science dawn and the technical college of calcium citrate with shell, [periodical name] journal .2010 of Zhanjiang Normal University, 31 (6) .-95-98[digests] take shell as raw material, adopt a calcination method to prepare calcium citrate, and utilize orthogonal experiment to be studied preparation condition. result shows: in 10mL mass concentration, be in 0.20g.mL-1 citric acid, add the oyster shell whiting after 1.0g calcining, neutralization reaction under 60 ℃ of conditions, the productive rate of products obtained therefrom is 94.04%, purity is 99.29%, product is through infrared and quality testing, substantially the quality requirement that meets China's calcium additive.

3, Chinese patent, application number: 92104844.0 applyings date: 1992.06.25 title: by the method for ordinary student lime and the medicinal calcium citrate of edible citric acid high-purity, open (bulletin) number: CN1066443, application (patent right) people: Hengda Trading Company, Chuansha, Shanghai, address: No. 242, Chuan Huan West Road, city proper and areas just outside its gates town, sea market Chuansha, invention (design) people: Yuan Jingcheng, summary, a kind of method of utilizing ordinary student lime and the medicinal calcium citrate of edible citric acid high-purity, technical characterictic is: by ordinary student lime and ammonium chloride and water wiring solution-forming by a certain percentage, after filtration, after clarification, pass into carbon dioxide and carry out carbonization, then through dehydration, washing, dehydration, dry, cooling, pulverize, screen to obtain powder A, again by the powder A after above-mentioned processing and edible citric acid and water wiring solution-forming by a certain percentage, react at a certain temperature, after question response finishes completely, through dehydration, washing, dehydration, dry, screen and obtain high purity medical calcium citrate.High purity medical calcium citrate, as a kind of good calcium tonic, has high medical value.

4, Chinese patent, application number: 201110233649.4 applyings date: 2011.08.16 title: the preparation method of high molten crystal formation calcium citrate, open (bulletin) number: CN102351688A open (bulletin) day: 2012.02.15 applies for (patent right) people: address, Heng Tong bio tech ltd, Shandong: industry park, Qinghe, Qinghe town, Huimin County, Accessories during Binzhou, Shandong Province invention (design) people: Wang Yuanda, summary, a kind of preparation method of high molten crystal formation calcium citrate.Technical scheme: formed by following steps: (one) raw material and proportioning: citric acid, calcium carbonate and 3.84: 3: 1 ratios of water mix; (2) after mixing, put into temperature and be the reactor of 20-50 ℃, start chemical reaction 50-60 minute; (3) shut down 25-35 minute, chemical reaction is ripe; (4) start 25-35 minute, emits the molten crystal formation calcium citrate of height under crystallization temperature; (5) packed products after filtering, drying.Beneficial effect: the molten crystal formation calcium citrate of synthetic height, molecular formula: Ca ₃h ₃(C ₆h ₅o ₇) ₂(HCO ₃) ₃, solubility 98%, is soluble calcium, replenishes the calcium and controls osteoporosis osteomalacia, humans and animals easily absorbs, and available calcium citrate injection and calcium citrate oral liquid, uses and is not subject to the restriction of indissoluble calcium citrate.

The preparation method of the calcium citrate that above-mentioned open source literature proposes, can not obtain dissolubility not only good, trap but also four high water citric acid calcium, generally just obtains ((C ₆h ₅o ₇) 2Ca ₃) H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 2H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 3H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂the mixture of O, for example document 1-3 utilizes eggshell or shell to produce calcium citrate, neutralization reaction is all added lime (calcium oxide), obtain containing ((C ₆h ₅o ₇) 2Ca ₃) H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 2H ₂o is more, and these calcium citrates are water-soluble better, but dissolving under one's belt and absorption bad; Document 4 mixes with citric acid, calcium carbonate and 3.84: 3: 1 ratios of water, 20-50 ℃ of reaction 50-60 minute; After chemical reaction maturation, obtain high molten crystal formation calcium citrate; (be actually containing ((C ₆h ₅o ₇) 2Ca ₃) H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 2H ₂the calcium citrate that O is more), at present bibliographical information is mostly thought ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂o absorbs bad (document 4 is also such discussion) to animal, and this is incomplete, should say, due to the calcium citrate except four crystallizations water, in the calcium citrate animal stomach of other crystallization water, absorbing bad (may be (C as injection ₆h ₅o ₇) 2Ca ₃) H ₂o, ((C ₆h ₅o ₇) 2Ca ₃) 2H ₂o is better.Concrete reason can provide at following beneficial effect of the present invention.

So, continuous progress along with society, human living standard improves constantly, people's environmental consciousness and legal consciousness constantly strengthen, country and the public also continue to increase the management intensity of animal feeding safety and degree of concern, therefore, explore a kind of animal calcium-supplementing preparation of safe, efficient, environmental protection, for improving China's animal husbandry integrated production capacity, improve agroecological environment, from source, control and guarantee food security, improve the survival and development of production of fodder industry, accelerate China's animal husbandry development, have positive realistic meaning.

Summary of the invention

The object of the invention is the above deficiency existing of pin and a kind of animal calcium-supplementing preparation safe, efficient, environmental protection is provided is calcium citrate organic feed additive and preparation method thereof, particularly organic feed additive of four crystallization water calcium citrates and preparation method thereof.

The present invention is achieved in that

The preparation method of the calcium citrate of four crystallizations water of the present invention is as follows:

Adopt following raw material and parts by weight: water: 60～80; Citric acid: 16～20; Precipitated calcium carbonate 10～15; Production stage:

(1) water is placed in reactor boiled;

(2) get citric acid and evenly drop into reactor, stir 3-10 minute to dissolving completely, keep 60-90 ℃; ,

(3) get precipitated calcium carbonate, slowly evenly drop into, stir, to complete reaction, obtain the calcium citrate ((C of four crystallizations water ₆h ₅o ₇) 2Ca ₃);

(4) precipitation: put into stainless steel pond cooling, precipitate;

(5) dehydration: the product of cooling precipitation is put into centrifuge dewatering;

(6) dry: the product of de-good water is introduced to pneumatic drier and be dried, baking temperature is controlled at 120 ℃～145 ℃;

(7) screening: dry cooling rear screening;

(8) packing of product after the assay was approved,, warehouse-in.

Chemical equation is:

C ₆H ₈O ₇+CaCO ₃→(C ₆H ₅O ₇) ₂Ca ₃·4H ₂O+CO ₂

Feed stripped consumption pig, ox, sheep is: perfect compound feed addition 3-5 kilogram per ton;

At poultry feed consumptions such as chicken and duck goose or rabbits, be: perfect compound feed addition 2-3 kilogram per ton;

Above-described citric acid is not contain the citric acid of heavy metal or harmful substance;

Above-described precipitated calcium carbonate (Light Calcium Carbonate) claim again winnofil (Precipitated Calcium Carbonate, be called for short PCC), not that common calcium carbonate stone is directly pulverized and obtained, but the raw material sections such as lime stone are burnt and generated lime and carbon dioxide, add again water digestion lime and generate milk of lime (main component is calcium hydroxide), and then pass into carbon dioxide carbonization milk of lime generation precipitation of calcium carbonate, finally by dewatering, be dried and pulverizing, make; Or first with sodium carbonate and calcium chloride, carry out metathesis reaction and generate precipitation of calcium carbonate, then through dewatering, be dried and pulverizing, make.It was 80 mesh sieves that the particle of precipitated calcium carbonate is controlled, and also can adopt micropowder light calcium carbonate (1～5 μ m) or fine and lightweight calcium carbonate (0.1～1 μ m).

The calcium citrate ((C of four crystallizations water that above-mentioned chemical equation obtains ₆h ₅o ₇) 2Ca ₃) 4H ₂o, primary first-order equation contains four crystallization water content more than 95%, the calcium citrate of a small amount of water, two water and three water, pH 5.5-7.5, is slightly soluble in water.

The method of inspection:

1, principle: in pH is greater than 12 medium, a Binding Reaction between Calconcarboxylic Sodium salt indicator directing terminal, with disodium ethylene diamine tetraacetate standard liquid titration calcium ion Ca ²⁺, excessive disodium ethylene diamine tetraacetate is captured the Ca with indicator complexing ²⁺, the indicator that dissociates, according to the terminal of change color judgement reaction.

2, analytical procedure:

Take approximately 0.2 gram, sample, be accurate to 0.0002 gram, be placed in 250 conical flasks, add 10ml water, 2ml hydrochloric acid solution, after dissolving to sample, be diluted with water to 100ml, add triethanolamine solution 5ml, sodium hydroxide solution 15ml, shake up, regulate pH to be greater than 13, add calcon-carboxylic acid 0.1g, with the titration of disodium ethylene diamine tetraacetate standard titration solution, to solution from aubergine, being become pure blue is terminal, carries out blank test simultaneously.

Disodium ethylene diamine tetraacetate standard titration solution: 0.05mol/l

Sodium hydroxide solution 1mol/l

Hydrochloric acid solution: 1+1

Triethanolamine solution: 30%

Calcon-carboxylic acid: take the sodium chloride that 10g is dried in advance at 105-110 ℃, be placed in mortar, add 0.1g calcon-carboxylic acid, porphyrize, mixes.

3. result is calculated

In sample, calcium citrate content represents with mass fraction %, by formula (1), calculates:

$X_1=\frac{(V_1-V_2)\&times;F\&times;8.307}{m_1\&times;1000\&times;(100-X_4)}\&times;100---\left(1\right)$

V ₁-titration sample consumes the volume of disodium ethylene diamine tetraacetate standard titration solution, and unit is milliliter (mL);

V ₂-titration blank solution consumes the volume of disodium ethylene diamine tetraacetate standard titration solution, and unit is milliliter (mL);

F-disodium ethylene diamine tetraacetate standard titration solution actual concentrations and 0.05 ratio;

The edetate of the every consumption of 8.037-1mL0.05mol/L is equivalent to the Ca (C of 8.037mg ₆h ₅o ₇) ₂;

M ₁the quality of-sample, unit is gram (g);

X ₄the loss on drying of-sample, %.

The mensuration of citric acid content in above-mentioned calcium citrate

1, principle, in acid solution, potassium permanganate can after having reacted, add KI quantitatively by citric acid oxidation, makes remaining KI reaction generate free-iodine, by sodium thiosulfate standard solution titration free-iodine, with this, calculates the content of citric acid.

Citric acid, anhydrous,

Hydrochloric acid solution: 1+1

Potassium permanganate: 0.1mol/l

Sodium thiosulfate standard solution 0.1mol/l

Sulfuric acid solution 20%

2, analytical procedure:

Take calcium citrate sample 1g, be accurate to 0.0002g, in 100mL beaker, add 10mL water and drip hydrochloric acid solution to sample and dissolve, move in 100mL volumetric flask, add water to scale, shake up; With pipette, pipette test solution 1.00mL, be placed in 250mL conical flask, add water 150mL, add sulfuric acid solution 10mL and manganese sulfate 1g, in water-bath, be heated to 70 ℃, under constantly shaking, slowly add Standard Potassium Permanganate Solution 25.0mL, in 70 ℃ of water-baths, place 10min, cooling with flowing water, add KI 2g, shake up, with sodium thiosulfate standard solution, be titrated to faint yellowly, add starch solution 2mL, continue to be titrated to blue disappearance for terminal, by (2) formula, calculate citric acid content.

$X_3=\frac{(25-K\&times;V_5)\&times;T\&times;100}{m_3\&times;(100-X_4)}\&times;100---\left(2\right)$

The volume of 25-Standard Potassium Permanganate Solution, unit is milliliter (mL);

The liquor potassic permanganate volume ratio that K-1mL sodium thiosulfate standard solution is suitable;

V ₅-burette test solution consumes sodium sulphate standard liquid volume ratio, and unit is milliliter (mL);

The anhydrous citric acid content that T-1mL Standard Potassium Permanganate Solution is suitable, unit is gram every milliliter (g/mL);

M ₃the quality of-sample, unit is gram (g);

X ₄the loss on drying of-sample, %.

The mensuration of above-mentioned calcium citrate and citric acid content is being write State Standard of the People's Republic of China, by the inventor, is write.

The invention has the beneficial effects as follows:

The present invention is a kind of animal calcium citrate organic feed additive of safe, efficient, environmental protection.The calcium citrate ((C of four crystallizations water ₆h ₅o ₇) 2Ca ₃) be slightly soluble in water, but under slightly acidic condition, solubility property is good, and animal trap is high.

Why the calcium citrate ((C of four crystallizations water ₆h ₅o ₇) 2Ca ₃) 4H ₂o is slightly soluble in water, but solubility property is good under slightly acidic condition, is animal trap high? mainly that the calcium citrate that contains 1-3 the crystallization water is easy to water-soluble, when water-soluble time, just become ionic condition, and the calcium of ionic condition absorbs not as organic calcium good absorbing, the calcium citrate ((C of four crystallizations water of the present invention ₆h ₅o ₇) 2Ca ₃) 4H ₂o is ionic condition, but organic complex, after entering in animal stomach, generates absorbable organic calcium with hydrochloric acid in gastric juice slow reaction, rather than ionized calcium, so the food and medicine standard of the U.S. is with ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂o, as calcium tonic, does not adopt the calcium citrate of 1-3 the crystallization water, may be exactly this reason.

The inventor thinks that the calcium citrate of high-dissolvability of background technology Introduction of Literatures can not make animal have good trap, is exactly above-mentioned reason.

In addition, the present invention is mainly to control reaction temperature and keeps 60-90 ℃, reaction time 0.5-3 hour and baking temperature to be controlled at 120 ℃～145 ℃, just can guarantee to obtain ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂o is more than 95%.

Accompanying drawing explanation

Fig. 1 is calcium citrate organic feed additive flow process figure of the present invention.

As shown in the figure, calcium citrate production method of the present invention is that water is placed in reactor boiled; Get again citric acid and evenly drop into reactor, stir 3-10 minute to dissolving completely, keep 60-90 ℃; Then get precipitated calcium carbonate, slowly evenly drop into, stir, to complete reaction, obtain the calcium citrate ((C of four crystallizations water ₆h ₅o ₇) 2Ca ₃) 4H ₂o; Through precipitation, dehydration, dry; , screening, check, packing, obtain product.

The specific embodiment

Embodiment 1:

In reactor, drop into 60 parts, water boiled, get 16 parts of citric acids and evenly drop into reactor, stir 3-10 minute to dissolving completely; Then get 10 parts of the precipitated calcium carbonates of 80 mesh sieves, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Then put into stainless steel pond cooling, precipitation.The product of cooling precipitation is put into centrifuge dewatering; Again the product of de-good water is introduced to pneumatic drier and be dried, baking temperature is controlled at 120 ℃～145 ℃, and dry cooling rear screening, after the assay was approved, is packaged to be product ((C ₆h ₅o ₇) 2Ca ₃) 4H ₂o, content is 96%.

Embodiment 2:

In reactor, drop into 70 parts, water boiled, get 18 parts of citric acids and evenly drop into reactor, stir 3-10 minute to dissolving completely; Then get 12 parts of the precipitated calcium carbonates of 80 mesh sieves, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Then put into stainless steel pond cooling, precipitation.The product of cooling precipitation is put into centrifuge dewatering; Again the product of de-good water is introduced to pneumatic drier and be dried, baking temperature is controlled at 120 ℃～145 ℃, and dry cooling rear screening, after the assay was approved, is packaged to be product (C ₆h ₅o ₇) 2Ca ₃) 4H ₂o, content is 97%.

Embodiment 3:

In reactor, drop into 80 parts, water boiled, get 20 parts of citric acids and evenly drop into reactor, stir 3-10 minute to dissolving completely; Then get 15 parts of the precipitated calcium carbonates of 80 mesh sieves, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Then put into stainless steel pond cooling, precipitation.The product of cooling precipitation is put into centrifuge dewatering; Again the product of de-good water is introduced to pneumatic drier and be dried, baking temperature is controlled at 120 ℃～145 ℃, and dry cooling rear screening, after the assay was approved, is packaged to be product (C ₆h ₅o ₇) 2Ca ₃) 4H ₂o, content is 96%.

Product quality indicator:

Project	Index
		Calcium citrate (in Ca3 (C6H5O7) 2) content, %	≥97.0
Calcium (in Ca) content, %	≥23.40
		Loss on drying, %	≤13.0
Total arsenic (in As), mg/kg	≤5.0
		Plumbous (in Pb), mg/kg	≤10.0
Mercury (in Hg), mg/kg	≤0.5
		Cadmium (in Cd), mg/kg	≤2.0
Chromium (in Cr), mg/kg	≤10.0

Practical function

One, the calcium citrate feeding experiment of four crystallizations water

Nanjing Zeweier Feed Co., Ltd. is the impact on breeding performonce fo animals with regard to feed addictive calcium citrate, entrusts Animal nutrition research institute of Sichuan Agricultural University to carry out zoopery, and the biological value of feed addictive calcium citrate is evaluated.Result of the test is as follows: (for convenient, the calcium citrate using is that the calcium citrate of four crystallizations water is all referred to as calcium citrate)

(1) experiment material: the calcium citrate of experimental group is Nanjing Zeweier Feed Co., Ltd.'s self-control; Positive control group precipitated calcium carbonate is commercially available feed grade additive.

(2) experimental animal and grouping:

Select 90 (body weight: 7.0 ± 0.5kg) of 21 age in days weanling pig.Wherein 84 are divided into 14 processing at random, and each processes 3 repetitions, and each repeats 2 pigs.Remain 6 pigs, be assigned randomly to calcium level and be NRC standard (Ca 0.8%) 2 processed group respectively repeat each 1.

(3) experimental design:

(4) test daily ration: basal diet forms and trophic level

Raw material	Basal diet (%)
		Corn	29.39
Popcorn	22.39
		Expanded soybean	10.00
Dregs of beans	10.00
		FSPC	5.00
Fish meal	5.00
		Whey powder	10.00
Sucrose	1.50
		Glucose	1.50
Bentonite	3.33

Sodium dihydrogen phosphate	0.33
		Salt	0.35
DL-METHIONINE	0.07
		FE-5	0.34
Threonine	0.11
		Tryptophan	0.04
Choline	0.10
		Add in ore deposit	0.50
Multidimensional	0.05
		Sulfuric acid Bacillus adhaerens (10%)	0.002
Add up to	100
		Trophic level (%)
Crude protein CP	19.83
		Digestible energy DE (MJ/kg)	14.09
Calcium Ca	0.37
		Total phosphorus	0.60
Available phosphorus	0.40
		Total lysine Lys	1.34
Can digestible lysine D-Lys	1.19
		Total sulfur-containing amino acid DSAA	0.68
Threonine	0.74
		Tryptophan	0.22

(5) feeding and management

Test is carried out at Animal nutrition research institute of Sichuan Agricultural University test site piglet nursing shed.Nursery house adopts slatted floor child care equipment, and house temperature control is at 22～25 ℃, and relative humidity is controlled at 65%～70%.Test is cleaned thoroughly, washes away and sterilize pig house and the various utensil of feeding the last week, sprays the facilities such as ground, fence, trough with caustic soda.Daily pig house sterilization Peracetic acid.Duration of test keeps colony house to ventilate, clean, be dried.Raise in advance 3 days, just trying phase 35d.Examination pig day is fed 4 times (8:00,12:00,16:00,20:00), and the amount of feeding shows a small surplus and is limited to eat rear hopper, freely drinks water.

(6) testing index and method

1. weaned piglets 4. 6. 7.

Feed intake, daily gain, feedstuff-meat ratio:

Just try phase 28d and weighing, recording feed addition every day.Calculate average daily ingestion amount, average daily gain, average daily ingestion amount/average daily gain calculating feedstuff-meat ratio.

Scours index: diarrhoea head is multiplied by corresponding diarrhoea score and calculates.

2. blood sample:

Off-test, after early 8:00 weighs on an empty stomach to examination pig, all pigs are taken a blood sample, separation of serum.Measure Ca, P, alkaline phosphatase activities in serum.

3. Carcass Index: test 8d is 8:00 early, in Ca 0.8% horizontal group, chooses at random 4 piglets for every group and butchers.

Shin bone index: measure calcium, phosphorus and shin bone ash content in shin bone, without the mensuration of fat dry and bone density, shin bone volume, shin bone breaking force.

Stomach and enteron aisle pH: after butchering end, with the direct insertion pH meter of pH90 type, measure immediately the pH value of stomach, jejunum, ileal contents.

4. metabolic test

Just trying early 8:00 of phase 29d, except Ca 0.6%, Ca 1.0% horizontal group, all the other each levels are selected 3 health, are approached average weight piglet, close in metabolic cage separately respectively, entirely receive excrement, urine.Experimental period 4d.Examination pig feed intake is in growth test, to pat 90% of equal feed intake everywhere, once claims sufficient 4d material amount, freely drinks water.Add up feed intake, defecation amount and the amount of urinating every day, in excrement and urine, add respectively 10% sulfuric acid (excrement adds 10ml by 100g, and urine adds 10ml by 100ml).Sample is placed in 0～4 ℃ of refrigerator in time.During due-in assembly bundle, the excrement of same pig, urine are concentrated and mixed, get 1/10 sample.Excrement sample dries 24h at 65 ℃, baking oven, under room temperature, places after 6h, pulverizes and makes air-dry sample, is placed in-20 ℃ of Refrigerator stores, to be analyzed.

Pig manure, urine samples: the calcium determinating reagent box that titration of potassium permanganate excrement calcium content, urine calcium adopt Nanjing to build up company is measured, and phosphomolybdic acid method is measured phosphorus content in fecaluria.

Calcium apparent digestibility (%)=(calcium is taken in the discharge rate of total amount-excrement calcium)/calcium is taken in total amount * 100

Calcium Apparent Availability (%)=[calcium is taken in total amount-(discharge rate+urine calcium discharge rate of excrement calcium)] * 100

Phosphorus apparent digestibility (%)=(phosphorus is taken in the discharge rate of total amount-excrement phosphorus)/phosphorus is taken in total amount * 100

Phosphorus Apparent Availability (%)=[phosphorus is taken in total amount-(discharge rate+urine phosphorus discharge rate of excrement phosphorus)] * 100

5. data analysis

Test data is carried out preliminary treatment with Excel.After 7d butchers, alimentary canal content pH value adopts SAS9.0 statistical software to carry out paired sample T check.Other data acquisition carries out two factor variance analyses with SAS9.0 statistical software, and Duncan method is carried out multiple ratio.Result represents by average ± standard deviation, and P < 0.05 thinks statistical significance.

(7) experimental result

1. Different Calcium Sources and the level impact on weaned piglets in diet

Note: colleague's data mark different lowercases and represent surprised significantly (P < 0.05), same letter or without letter representation difference not significantly (P > 0.05)

The processed group of calcium carbonate as calcium source take in 1:T representative;

The processed group of calcium citrate as calcium source take in 2:N representative.

3:ADG: average daily gain; ADFI: average feed intake; F/G: feedstuff-meat ratio.

As seen from the above table, the rising along with Dietary Calcium level in 0-14 days, the average daily gain of piglet and feed intake all present the trend that first raises and reduce afterwards, and material anharmonic ratio is irregular variation.In calcium carbonate group, average daily gain is the highest with 0.8% group of Ca; 0.6% group of feed intake Ca is the highest, but approaches with 0.8% group of Ca; 0.8% group of feedstuff-meat ratio Ca is minimum.In calcium citrate group, average daily gain is the highest with 0.8% group of Ca; 0.8% group of feed intake Ca is the highest; 0.8% group of feedstuff-meat ratio Ca is minimum.Above-mentioned indices is difference not significantly (P > 0.05) all.Between calcium carbonate and calcium citrate group, relatively, piglet average daily gain, feed intake calcium citrate Ca0.8% group are higher than other each group of calcium carbonate, but there was no significant difference (P > 0.05); 0.8% group of feedstuff-meat ratio calcium citrate Ca is lower than each group of calcium carbonate but difference not significantly (P > 0.05).Comprehensive each index of weaned piglets is thought: 21 age in days weanling pig daily rations be take calcium carbonate during as calcium source, suitable calcium level is 0.8%, take calcium citrate during as calcium source suitable calcium level be 0.8%, and comprehensively the known calcium citrate of each index than the calcium carbonate calcium source as piglet preferably.Can improve the growth performance of piglet.

2. Different Calcium Sources and the level impact on grice diarrhoea rate in diet

From upper table 5, in calcium carbonate group and in calcium citrate group grice diarrhoea index 14-28d lower than 0-14d, but there was no significant difference (P > 0.05).In calcium carbonate group, along with the rising of calcium carbonate levels, Scours index presents the trend of rising, but there was no significant difference; In calcium citrate group Scours index minimum be Ca0.6% group but with Ca0.8% there was no significant difference (P > 0.05).Data in table, calcium citrate group grice diarrhoea index, lower than calcium carbonate group, is organized significantly lower than each group of calcium carbonate (P < 0.05) at 0-14d calcium citrate group Ca0.6%; At 14-28d, all there were significant differences (P < 0.05) for each group of calcium citrate each group and calcium carbonate.

3. the impact of Different Calcium Sources on pH value in piglet alimentary canal in diet

Project	Calcium carbonate Ca 0.8% level	Calcium citrate Ca 0.8% level
			Stomach pH	3.18±0.63	2.19±0.54**
Jejunum pH	6.52±0.24	6.57±0.27
			Ileum pH	7.52±0.30	7.18±0.29**

As the table shows, calcium citrate Ca0.8% group piglet stomach and jejunum pH organize piglet stomach with calcium carbonate Ca0.8% and jejunum pH has utmost point significant difference (P < 0.05), and two groups of piglet ileum pH values are without significant difference (P < 0.05).

4. diet Different Calcium Sources and the level impact on piglet blood biochemical indicator

Note: show significant difference (P < 0.05) with the different lowercase alphabets of row labels, represent difference extremely significantly (P < 0.01) with the different capitalizations of row labels;

The processed group of calcium carbonate as calcium source take in 1:T representative;

The processed group of calcium citrate as calcium source take in 2:N representative.

As above represent, serum calcium cancentration, in calcium carbonate processed group, Ca0.8% horizontal group serum calcium cancentration is higher than other each level, but each calcium level is without significant difference (P > 0.05).In calcium citrate is processed, Ca0.9% horizontal group is significantly higher than other each calcium level group (P < 0.05), and all the other each levels are without significant difference (P > 0.05).Calcium citrate and calcium carbonate comparison, calcium citrate Ca0.9% horizontal group is significantly higher than each calcium level group of calcium carbonate (P < 0.05), and all the other are without significant difference (P > 0.05).Serum inorganic phosphorus concentration, first raises and reduces afterwards with Dietary Calcium level.Serum inorganic phosphorus concentration raises with calcium level, the trend that presenting first raises reduces afterwards.In calcium carbonate processed group, Ca0.9% horizontal group serum inorganic phosphorus concentration is significantly higher than other each level (P < 0.05), and other each group level is without significant difference (P > 0.05).In calcium citrate is processed, Ca0.9%, Ca0.6% horizontal group are significantly higher than Ca1.0%, Ca1.1% calcium level group (P < 0.05), and other each group level is without significant difference (P > 0.05).Calcium citrate and calcium carbonate process between comparative result show, two calcium sources at Ca0.9% higher than other each group, but without significant difference (P > 0.05).Serum alkaline phosphatase activity Ca0.9% level in calcium carbonate group is significantly higher than other each group (P < 0.05), in calcium citrate group, Ca0.8% level is significantly higher than other each group (P < 0.05), and the two is without significant difference (P > 0.05).Comprehensively Biochemical Indices In Serum is thought, Dietary Calcium level is better with 0.9%.

This result of the test shows, meets the calcium requirement of 7-8kg weanling pig optimum growh needs, and calcium carbonate is Ca0.9%, calcium citrate Ca0.8%.And find that by slaughter experiment calcium citrate has extremely significantly reduced piglet stomach inner pH value, reduce grice diarrhoea rate, thereby improved weaned piglets.By blood parameters, find that calcium phosphorus utilization two calcium sources all reach the highest at Ca0.9%, but calcium citrate group is significantly higher than calcium carbonate group.Alkaline phosphatase activities calcium carbonate group reaches the highest when Ca0.9%, and calcium citrate group reaches the highest when Ca0.8%, shows that in two, calcium source is respectively when this two calcium levels, and piglet bone growth metabolism is the most active.Comprehensive the above results, meets the calcium level of 7-8kg weanling pig optimum growh, and calcium carbonate is Ca0.9%, calcium citrate Ca0.8%.And calcium citrate can improve the production performance of piglet.Therefore, piglet produce in calcium citrate be than the calcium carbonate calcium source of high-quality more.

Two, the effect comparison that four water citric acid calcium of the present invention and ordinary calcium carbonate (limestone powder), the calcium citrate (abbreviation ionized calcium) for preparing with milk of lime adding citric acid are fed piglet

Select 50 of 25 age in days weanling pigs (initial body weight: 8.0 ± 0.5kg), be divided at random 3 groups, the present invention's four water citric acid calcium, each group of ordinary calcium carbonate and abbreviation ionized calcium, same feed, same nursing way to manage, feed one month, measure the calcium in piglet blood, the calcium content of four water citric acid calcium is the highest as a result, being called for short ionized calcium takes second place, what content was minimum is ordinary calcium carbonate, piglet outward appearance: four water citric acid calcium hair colors of the present invention are bright, disposition is active, feed the average weight of month than other two groups of weights, that than ordinary calcium carbonate, feeds is heavy 2 kilograms, that than ionized calcium, feeds is heavy 1 kilogram.

Claims (3)

1. a production method for calcium citrate organic feed additive, contains the calcium citrate that main component is four crystallizations water, and the preparation process of the calcium citrate of four crystallizations water is as follows:

Adopt following raw material and parts by weight: water: 60～80; Citric acid: 16～20; Precipitated calcium carbonate 10～15; Production stage:

(1) water is placed in reactor boiled;

(2) get citric acid and evenly drop into reactor, stir 3-10 minute to dissolving completely, keep 60-90 ℃;

(3) get precipitated calcium carbonate, slowly evenly drop into, stir, to complete reaction, obtain the calcium citrate ((C of four crystallizations water ₆h ₅o ₇) 2Ca ₃) 4H ₂o;

(4) precipitation: put into stainless steel pond cooling, precipitate;

(5) dehydration: the product of cooling precipitation is put into centrifuge dewatering;

(6) dry: the product of de-good water is introduced to pneumatic drier and be dried, baking temperature is controlled at 120 ℃～145 ℃;

(7) screening: dry cooling rear screening;

(8) check, packing;

Described precipitated calcium carbonate is that limestone calcination is generated to lime and carbon dioxide, then adds water digestion lime generation milk of lime, and then passes into carbon dioxide carbonization milk of lime generation precipitation of calcium carbonate, finally by dewatering, be dried and pulverizing, makes; Or first with sodium carbonate and calcium chloride, carry out metathesis reaction and generate precipitation of calcium carbonate, then through dewatering, be dried and pulverizing, make; The grain fineness of described precipitated calcium carbonate is crossed 80 mesh sieves.

2. the production method of calcium citrate organic feed additive according to claim 1, it is characterized in that: the assay of calcium citrate is: take approximately 0.2 gram, sample, be accurate to 0.0002 gram, be placed in 250 conical flasks, add 10ml water, 2ml hydrochloric acid solution, after dissolving to sample, be diluted with water to 100ml, add triethanolamine solution 5ml, sodium hydroxide solution 15ml, shake up, regulate pH to be greater than 13, add calcon-carboxylic acid 0.1g, with the titration of disodium ethylene diamine tetraacetate standard titration solution, to solution from aubergine, being become pure blue is terminal.

3. the production method of calcium citrate organic feed additive according to claim 1, it is characterized in that: in calcium citrate, the mensuration of citric acid content is to take calcium citrate sample 1g, be accurate to 0.0002g, in 100mL beaker, add 10mL water and drip hydrochloric acid solution to sample and dissolve, move in 100mL volumetric flask, add water to scale, shake up; With pipette, pipette test solution 1.00mL, be placed in 250mL conical flask, add water 150mL, add sulfuric acid solution 10mL and manganese sulfate 1g, in water-bath, be heated to 70 ℃, under constantly shaking, slowly add Standard Potassium Permanganate Solution 25.0 mL, in 70 ℃ of water-baths, place 10min, cooling with flowing water, add KI 2g, shake up, with sodium thiosulfate standard solution, be titrated to faint yellowly, add starch solution 2mL, continue to be titrated to blue disappearance for terminal, by calculating citric acid content.