CN104356035A - Preparation method for 2-hydroxy-4-methylthio-calcuim butyrate - Google Patents
Preparation method for 2-hydroxy-4-methylthio-calcuim butyrate Download PDFInfo
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Abstract
The invention discloses a preparation method for 2-hydroxy-4-methylthio-calcuim butyrate. The method is characterized by comprising the following step of reacting reaction raw materials comprising a 2-hydroxy-4-methylthio-butyric acid solution and one or more of calcium hydroxide, calcium oxide and calcium carbonate with ammonium bisulfate introduced as an organic reaction catalyst to obtain the 2-hydroxy-4-methylthio-calcuim butyrate. The method has the advantages of being mild in reaction, free of specific stirring tools, high in universality, less in equipment investment, low in production cost, convenient to use, mild and controllable in the whole reaction process, low in probability of product decomposition or coking rate, complete in reaction, time-saving, high in product yield, purity and yield, energy-saving and more environment-friendly.
Description
Technical field
The present invention relates to food or method for producing feed additive technical field, be specifically related to the preparation method of a kind of 2-2-hydroxy-4-methylthio-Calcium Butyrate.
Background technology
2-amino-4-methvlsulfanyl-butyric acid, is commonly called as methionine hydroxy calcium (CAS No.4857-44-7); Often be used in animal-feed as amino acids fodder additives, it is a kind of animal growth promoter, for the synthesis of protein, can improve growth of animal rate and laying rate of poultry, but traditional methionine(Met) preparation method, see the Chinese patent " preparation method of methionine(Met) " that the patent No. is 99107001.1, it is under salt of wormwood existent condition, 5-glycolylurea is hydrolyzed, then in hydrolyzed solution, pass into carbonic acid gas neutralization, make methionine(Met) crystallization.But this technique has the shortcomings such as investment of production is huge, apparatus expensive, technical sophistication, process line are long, production cost is high, so be not a kind of method of economy.
There are scientific and technical personnel to develop methionine(Met) similar compound as 2-2-hydroxy-4-methylthio-Calcium Butyrate for this reason, see the Chinese patent " a kind of preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate " that the patent No. is 02137790.1, its technical process for add calcium oxide or calcium hydroxide in combination drying machine, adopt continuous small dose to add 2-2-hydroxy-4-methylthio-butyric acid solution subsequently, make it that neutralization reaction occur and generate 2-2-hydroxy-4-methylthio-Calcium Butyrate.2-2-hydroxy-4-methylthio-Calcium Butyrate trade(brand)name is methionine hydroxy calcium again, as amino acids fodder additives, it is a kind of origin of amino acid of brilliance, effectively can be converted into methionine(Met) in animal body, for the synthesis of protein, improve growth of animal rate and laying rate of poultry, and be again a kind of organic calcium of high-quality simultaneously, for animal growth provides the calcium source of high-quality, there is good economic benefit.The preparation method of this 2-2-hydroxy-4-methylthio-Calcium Butyrate has the advantages such as technical process is short, facility investment is few, production cost is low, and finished product is pressed powder, easy to use, wide application, without the need to Special feeding system, is a kind of excellent methionine(Met) substitute.But, there is following defect in the preparation method of above-mentioned 2-2-hydroxy-4-methylthio-Calcium Butyrate: is difficult to mix when the calcium oxide of solid state or calcium hydroxide start with the 2-2-hydroxy-4-methylthio-butyric acid of liquid state, reaction is also difficult to, but once both react, reaction will be very violent, speed of response is very fast again, the pressure in reaction vessel can be made to increase sharply on the one hand, and produce a large amount of heats, thus cause speed of response, pressure and temperature is difficult to control, and after temperature is greater than 130 degree, product 2-2-hydroxy-4-methylthio-Calcium Butyrate can occur to decompose or coking, on the other hand, part material (as calcium oxide or calcium hydroxide or intermediate product etc.) is as easy as rolling off a log is packed to agglomerate or bulk, fully cannot participate in reaction, cause reaction raw materials amount relative deficiency, react insufficient, intermediate product is more, product purity is not high, thus affect efficiency of pcr product and quality.And after material is packed to agglomerate or bulk, the moisture content of the inside is difficult to be evaporated when drying, affects material volume drying, makes the dry materials time greatly extend, and causes the whole production time long, have impact on output.
In 2012.3.30, applicant has applied for that application number is 2012100885716, name is called " a kind of preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate ", in the disclosure in this patent, applicant reacts violent in order to the 2-2-hydroxy-4-methylthio-butyric acid of the calcium oxide or calcium hydroxide and liquid state that overcome solid state, speed of response produces a large amount of heats again very soon, thus cause speed of response, the unmanageable deficiency of pressure and temperature, have employed skim-cutter type mixing drying machine to strengthen stirring intensity, strict control material order of addition(of ingredients) and temperature of reaction is adopted to prevent coking, but technique scheme still has the following disadvantages: 1. first, although the reacting phase of the 2-2-hydroxy-4-methylthio-between butyric acid and calcium carbonate in later stage is to mitigation in this application, but the vigorous reaction of calcium hydroxide or calcium oxide and 2-2-hydroxy-4-methylthio-butyric acid is still inevitable in earlier stage, still there is temperature of reaction high, easily cause the risk of product coking, therefore adopt the strong skim-cutter type mixing drying machine of stirring dynamics to make reacting phase to mitigation, but this just causes and must use specific skim-cutter type mixing drying machine, poor universality, the deficiency that operating restraint is narrow, 2. secondly, this reacting drying time is long, the production cycle of prolongation, certainly will cause the deficiency of the high length consuming time of cost to the producer, 3. the poorly soluble problem between the 2-2-hydroxy-4-methylthio-butyric acid of solid-state calcium hydroxide or calcium oxide or calcium carbonate and liquid still exists, and raw material will certainly be caused to lump, and reacts insufficient not enough thoroughly, 4. due to calcium hydroxide or the vigorous reaction of calcium oxide and 2-2-hydroxy-4-methylthio-butyric acid in early stage, cause whole speed of reaction and the time wayward, the easy pyrolytic decomposition of product.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, there is provided a kind of reaction temperature and, do not need specific stirring tool, highly versatile, facility investment be few, production cost is low, easy to use, whole reaction process is gentle, controlled, not easily causes decomposition product or coking, reacts completely, saves time, efficiency of pcr product is high, purity is high, output is high and the preparation method of the 2-2-hydroxy-4-methylthio-Calcium Butyrate of energy-conserving and environment-protective more.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate, the method comprises: using one or more in 2-2-hydroxy-4-methylthio-butyric acid solution and calcium hydroxide, calcium oxide, calcium carbonate as reaction raw materials, introduce monoammonium sulfate as the catalyzer of organic reaction, then carry out being obtained by reacting 2-2-hydroxy-4-methylthio-Calcium Butyrate.
The preparation method of the above-mentioned concrete 2-2-hydroxy-4-methylthio-Calcium Butyrate of the present invention, be specially: first monoammonium sulfate is added in 2-2-hydroxy-4-methylthio-butyric acid solution, then, add in calcium hydroxide, calcium oxide, calcium carbonate in stirrer or mixing machine or reactor one or more, subsequently, the 2-2-hydroxy-4-methylthio-butyric acid solution added containing monoammonium sulfate carries out reaction and produces;
Or
First monoammonium sulfate is added in 2-2-hydroxy-4-methylthio-butyric acid solution, then, 2-2-hydroxy-4-methylthio-butyric acid the solution containing monoammonium sulfate is added in stirrer or mixing machine or reactor, subsequently, add in calcium hydroxide, calcium oxide, calcium carbonate one or more carry out reaction and produce;
Or
First in stirrer or mixing machine or reactor, add 2-2-hydroxy-4-methylthio-butyric acid solution, then, add monoammonium sulfate, subsequently, one or more adding in calcium hydroxide, calcium oxide, calcium carbonate carry out reaction production.
In the method that the present invention is above-mentioned, reaction process is that limit is stirred (or mixing) limit reaction or do not need to stir direct reaction, and reaction in General reactions 10-15 minute just can terminate.
Also comprise at 100-130 degree temperature dry 20 ~ 30 minutes again after the present invention's reaction terminates, within making material reach the water content 5% of regulation, eventually pass cooling, pulverizing, sieve, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate.
The add-on of the monoammonium sulfate that the present invention is above-mentioned is 0.1 ‰-1% of 2-2-hydroxy-4-methylthio-butyric acid weight in 2-2-hydroxy-4-methylthio-butyric acid solution.
Above-mentioned raw material can be that calcium hydroxide or one of calcium oxide or calcium carbonate react with 2-2-hydroxy-4-methylthio-butyric acid solution, also can be that both or the three's mixing (arbitrarily than mixing) in calcium hydroxide or calcium oxide or calcium carbonate reacts with 2-2-hydroxy-4-methylthio-butyric acid solution together.
The mole number sum of the mole number of the calcium hydroxide that the present invention is above-mentioned or calcium oxide or calcium carbonate or both and above mixing equals the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution, and the raw material reaction that participation can be made to react like this is complete.
The concentration of 2-2-hydroxy-4-methylthio-butyric acid solution that the present invention is above-mentioned is the mass percent of 50 ~ 95%, and this concentration requirement, to improve yield and the purity of product, is enhanced productivity.In addition, the present invention adds the catalyzer of monoammonium sulfate as organic reaction due to creationary, compared with being the mass percent of 80 ~ 90% with the concentration of traditional 2-2-hydroxy-4-methylthio-butyric acid solution, its mass percent concentration scope is wider, overcome tradition lower than less than 80% the shortcoming that can not react of concentration, therefore, applied range, also more loose to ingredient requirement.
The above-mentioned reaction of the present invention adopts stirrer or mixing machine or reactor, and Simplified flowsheet step, reduces production cost.
Compared with prior art, the present invention has following remarkable advantage and beneficial effect:
(1) reaction raw materials of the present invention is 2-2-hydroxy-4-methylthio-butyric acid and calcium hydroxide or calcium oxide or calcium carbonate, under the catalysis of monoammonium sulfate, reaction continues, gentle, to continue relative to the reaction of 2-2-hydroxy-4-methylthio-butyric acid and calcium hydroxide or calcium oxide, much gentle, the W-response speed of this reaction is continued than the reaction of calcium hydroxide in prior art or calcium oxide and 2-2-hydroxy-4-methylthio-butyric acid, ease too much, so the temperature of reaction in stirrer or mixing machine or reactor can not be very high, product 2-2-hydroxy-4-methylthio-Calcium Butyrate can not occur to decompose or coking.
(2) the present invention is under the katalysis of monoammonium sulfate, react more orderly, fully, completely, make whole mixture internal loose, good fluidity, more orderly than the reaction of calcium hydroxide in prior art or calcium oxide and 2-2-hydroxy-4-methylthio-butyric acid, completely many, solve that a part of material in prior art (as calcium oxide or calcium hydroxide or intermediate product etc.) is as easy as rolling off a log is packed to agglomerate or bulk preferably, fully cannot participate in reaction, cause reaction raw materials amount relative deficiency, react insufficient, intermediate product is more, product purity is not high, thus affect the problems such as efficiency of pcr product and quality, also overcome traditional method due to reaction mass easily forms bulk simultaneously, and material hardness is high, volume large, is easy in stirring or crushing process defect machine being caused to damage and fracture, the present invention adds that the material of catalyzer is looser, good fluidity, can not cause damage to machine.
(3) the present invention adds monoammonium sulfate as after catalyzer, because reaction bulk velocity is relatively more orderly, mitigation, making 2-2-hydroxy-4-methylthio-butyric acid add speed can be much faster than prior art, so the whole reaction times is also much fast than prior art, at least shorten more than 1/2nd.As from the foregoing, the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate of the present invention except there is the features such as technical process is short, facility investment is few, production cost is low, easy to use, also have that reaction continues gentleness, energy-conserving and environment-protective, product can not occur to decompose or coking, reaction in order, fully, complete, save time, efficiency of pcr product is high, purity is high, output advantages of higher.
(4) the present invention first using monoammonium sulfate as catalyst application in the preparation of 2-2-hydroxy-4-methylthio-Calcium Butyrate, this catalyzer low price, easy acquisition, easy to use, comparatively fast can be separated with product in reaction process, can reuse through condensation after being evaporated, cost is very low.Because the solubleness of catalyzer of the present invention in 2-2-hydroxy-4-methylthio-butyric acid solution is very big, therefore, be easy to solve homogeneously in 2-2-hydroxy-4-methylthio-butyric acid aqueous solution; This catalyzer due to can solve homogeneously in 2-2-hydroxy-4-methylthio-butyric acid aqueous solution therefore enable reaction rapidly, multiple spot, to start simultaneously, solve preferably when the calcium oxide of solid state in prior art or calcium hydroxide start with the 2-2-hydroxy-4-methylthio-butyric acid of liquid state and be difficult to carry out mixing, reacting the problem be also difficult to; Carry out equilibrium, sustained reaction at a lot of point on the other hand simultaneously, substantially increase the reaction overall rate of 2-2-hydroxy-4-methylthio-butyric acid and calcium hydroxide or calcium oxide or calcium carbonate, make reaction more completely, thoroughly simultaneously; Owing to reacting thorough, product loosens, does not lump, and product drying is also more thorough, and also greatly shortens the time of drying making material follow-up.
Embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
(1) first monoammonium sulfate is added in 2-2-hydroxy-4-methylthio-butyric acid solution and mixes, monoammonium sulfate add-on be 2-2-hydroxy-4-methylthio-butyric acid weight 1%, 2-2-hydroxy-4-methylthio-butyric acid solution quality very concentration be 80%;
(2) then in stirrer or mixing machine or reactor, add calcium hydroxide, then the mixture of step (1) is joined in stirrer or mixing machine or reactor and fully react with calcium hydroxide; Calcium hydroxide is 1:1 with the ratio of the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution.
(3) reaction after terminating at 100-130 degree temperature dry 20 ~ 30 minutes again, within making material reach the water content 1% of regulation, eventually passes cooling, pulverizing, sieves, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate.Yield is more than 95%.
Embodiment 2
(1) in stirrer or mixing machine or reactor, first add 2-2-hydroxy-4-methylthio-butyric acid solution and monoammonium sulfate mixing that mass percent is 88%, the add-on of monoammonium sulfate is 0.1% of 2-2-hydroxy-4-methylthio-butyric acid weight;
(2) subsequently, add calcium oxide to produce; Calcium oxide is 1:1 with the ratio of the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution;
(3) reaction after terminating at 100-130 degree temperature dry 20 ~ 30 minutes again, within making material reach the water content 1% of regulation, eventually passes cooling, pulverizing, sieves, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate; Yield is more than 96%.
Embodiment 3
(1) first in stirrer or mixing machine or reactor, add 2-2-hydroxy-4-methylthio-butyric acid solution that mass percent is 88%, then, add monoammonium sulfate, the add-on of monoammonium sulfate is 0.1% of 2-2-hydroxy-4-methylthio-butyric acid weight;
(2) subsequently, add calcium hydroxide, calcium oxide and calcium carbonate to produce; The mole number of calcium hydroxide, calcium oxide and calcium carbonate three sum (three arbitrarily than) is 1:1 with the ratio of the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution;
(3) reaction after terminating at 100-130 degree temperature dry 20 ~ 30 minutes again, within making material reach the water content 1% of regulation, eventually passes cooling, pulverizing, sieves, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate; Yield is more than 97%.
Embodiment 4
(1) first in stirrer or mixing machine or reactor, add 2-2-hydroxy-4-methylthio-butyric acid solution that mass percent is 55%, then, add monoammonium sulfate, the add-on of monoammonium sulfate is 0.5% of 2-2-hydroxy-4-methylthio-butyric acid weight;
(2) subsequently, calcium hydroxide is added and calcium carbonate is produced; The mole number of calcium hydroxide and calcium carbonate sum (arbitrarily than) is 1:1 with the ratio of the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution;
(3) reaction after terminating at 100-130 degree temperature dry 20 ~ 30 minutes again, within making material reach the water content 1% of regulation, eventually passes cooling, pulverizing, sieves, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate; Yield is more than 95%.
Above-described embodiment 1-4 reaction process is violent, and reaction is mild, rapidly, time of drying is short, and material loosens, do not lump, good fluidity.
Claims (7)
1. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate, it is characterized in that, the method comprises: using one or more in 2-2-hydroxy-4-methylthio-butyric acid solution and calcium hydroxide, calcium oxide, calcium carbonate as reaction raw materials, introduce monoammonium sulfate as the catalyzer of organic reaction, then carry out being obtained by reacting 2-2-hydroxy-4-methylthio-Calcium Butyrate.
2. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 1, it is characterized in that, first monoammonium sulfate is added in 2-2-hydroxy-4-methylthio-butyric acid solution, then, add in calcium hydroxide, calcium oxide, calcium carbonate in stirrer or mixing machine or reactor one or more, subsequently, the 2-2-hydroxy-4-methylthio-butyric acid solution added containing monoammonium sulfate carries out reaction and produces;
Or
First monoammonium sulfate is added in 2-2-hydroxy-4-methylthio-butyric acid solution, then, 2-2-hydroxy-4-methylthio-butyric acid the solution containing monoammonium sulfate is added in stirrer or mixing machine or reactor, subsequently, add in calcium hydroxide, calcium oxide, calcium carbonate one or more carry out reaction and produce;
Or
First in stirrer or mixing machine or reactor, add 2-2-hydroxy-4-methylthio-butyric acid solution, then, add monoammonium sulfate, subsequently, one or more adding in calcium hydroxide, calcium oxide, calcium carbonate carry out reaction production.
3. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 2, is characterized in that, its reaction process of the reaction described in the method is reaction while stirring or reaction between not stirring, and reaction in 10-15 minute terminates.
4. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 3, it is characterized in that, also to comprise the steps: at 100-130 degree temperature after the method reaction terminates dry reaction terminate after gained material 20 ~ 30 minutes, within making material reach water content 5%, eventually pass cooling, pulverizing, screening, obtain 2-2-hydroxy-4-methylthio-Calcium Butyrate.
5. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 3, is characterized in that, the add-on of described monoammonium sulfate is 0.1 ‰-1% of 2-2-hydroxy-4-methylthio-butyric acid weight in 2-2-hydroxy-4-methylthio-butyric acid solution.
6. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 3, it is characterized in that, the mole number of described calcium hydroxide or calcium oxide or calcium carbonate or sum of the two or three's sum equals the mole number of 2-2-hydroxy-4-methylthio-butyric acid in 2-2-hydroxy-4-methylthio-butyric acid solution.
7. the preparation method of 2-2-hydroxy-4-methylthio-Calcium Butyrate according to claim 3, is characterized in that, the concentration of described 2-2-hydroxy-4-methylthio-butyric acid solution is the mass percent of 50 ~ 95%.
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| CN103467348A (en) * | 2013-10-08 | 2013-12-25 | 重庆紫光化工股份有限公司 | Preparation method of large-particle crystal type high-bulk-density calcium 2-hydroxy-4-(methylthio)butyrate |
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