CN1931844A - Prepn process of copper nicotinate - Google Patents
Prepn process of copper nicotinate Download PDFInfo
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- CN1931844A CN1931844A CN 200610124693 CN200610124693A CN1931844A CN 1931844 A CN1931844 A CN 1931844A CN 200610124693 CN200610124693 CN 200610124693 CN 200610124693 A CN200610124693 A CN 200610124693A CN 1931844 A CN1931844 A CN 1931844A
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- nicotinic acid
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Abstract
The preparation process of copper nicotinate includes the following steps: 1. adding nicotinic acid and water into reactor, and adding water soluble alkaline matter slowly via stirring until nicotinic acid is converted into salt dissolved in water completely; and 2. dissolving inorganic copper salt into water, dropping the water solution of inorganic copper salt into the water solution of the nicotinate slowly via stirring, regulating pH to 4-6 to separate blue or green blue precipitate; stilling to age, centrifuging or suction filtering to obtain the precipitate; washing the precipitate with water, centrifuging or suction filtering, and drying to obtain the copper nicotinate product. The preparation process has the advantages of fast reaction speed, environment friendship, low cost, high product yield, high product purity, etc. and the product has high bioavailability.
Description
Affiliated technical field:
The present invention relates to a kind of preparation method of copper nicotinate.
Background technology:
Found in feed, to add the copper (Cu) of 10 times of animal normal needs first in 1945 from Braude, can obviously improve since the production performance of animal, copper is widely used in pig industry as a kind of effective growth promoter, especially in the intensive culture process, brought into play huge effect to promoting growth of animal to improve production performance.But because present general CuSO
4, specific absorption is low, and residual plurality of heavy metal ion discharges Cu to environment in the ight soil
2+The ionic catalysis VITAMIN is decomposed, and can not directly mix in feed processing and storage process, improves feed processing and storage cost, is unsolved up to now a great problem.So high-copper when improving production performance, has also brought as the animal chronic poisoning, has improved feed cost, the wasting of resources and serious problem of environmental pollution.For increasing operation rate, reduce environmental pollution, seek efficient copper source and surrogate thereof, the copper content that reduces in the feed has caused people's common concern.
Summary of the invention:
The purpose of this invention is to provide a kind of processing method by preparation such as nicotinic acid, alkaline carbonate or alkali metal hydroxide and inorganic mantoquita copper nicotinate, promotes nuisanceless, the first-generation metal inner complex fodder additives full-scale development application of high absorption rate; Solve simultaneously in feed processing and the storage process trace element can't with the direct blended difficult problem of various VITAMIN, simplify feed, premixed feed production technique and condition of storage, reduce cost, help the development of relevant industries such as fodder industry; Improve the absorption rate of copper, reduce the discharging of copper, reduce environmental pollution, preserve the ecological environment.
Two reaction systems are arranged among the preparation technology of copper nicotinate: one is that organic solvent (as ethanol) is the reaction system of reaction medium, and another is to be reaction medium reaction system at normal temperatures and pressures with water.The reaction mechanism difference of the two, the former is to be the heterogeneous reaction of dispersion medium (copper sulfate is insoluble to ethanol) with ethanol, undertaken by reflux, long reaction time needs more than 5 hours, the product yield is (about 80%), product purity lower (92%), energy consumption height, facility investment height, complex process, the cost height:
The latter transfers nicotinic acid to water-soluble salt earlier, again with CuSO
4Reaction, nicotinic acid is pyridine-3-carboxylic acid, also claims vitamin PP, this is the process patent application content that the present invention now will declare.Entire reaction of the present invention is in the aqueous solution and carries out at normal temperatures and pressures.If do not add catalyzer, then speed of reaction is slow, needs 6～10 hours approximately, yield 91.2%, purity 93.6%.Add a spot of catalyzer such as the single nickel salt afterreaction carries out rapidly, make an appointment with reaction half an hour to finish, yield (＞96%) and purity (＞97%) height, and also reaction mother liquor is as the solvent of following secondary response, needn't add the catalyst sulfuric acid nickel reactant again and also can carry out rapidly, promptly catalyzer can be reused.Possible mechanism is Ni
2+With the nicotinate reaction tendency is little but speed is fast, and Cu
2+With the nicotinate reaction tendency is big but speed is slow, pass through Ni
2+Coordination causes, and then Cu
2+So in huge legendary turtle conjunction generation, is Ni
2+Played catalyzer:
Concrete processing step of the present invention is: 1) add nicotinic acid and an amount of water in reactor, under constantly stirring, slowly add an amount of solubility alkalescence material, solubility alkalescence material has a kind of soluble carbon hydrochlorate, solubility carbonic acid hydrogen salt, water-soluble alkali oxyhydroxide of being selected from least, general alkaline carbonate or supercarbonate or the oxyhydroxide of adopting, as yellow soda ash, sodium bicarbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, lithium hydroxide, preferred yellow soda ash or sodium hydroxide are till nicotinic acid all is dissolved into the nicotinate aqueous solution; 2) can add little amount of catalyst again, stirring and dissolving, catalyzer is selected from the transition metal water-soluble salt, preferably sulfuric acid nickel (if do not add catalyzer, speed is slow, and yield is relative with purity low, preferably adds catalyzer); 3) with the water-soluble inorganic mantoquita, have a kind of cupric sulfate pentahydrate, cupric chloride, cupric nitrate of being selected from least, preferably sulfuric acid copper, after being dissolved in a certain amount of water, this aqueous solution is slowly joined in the above-mentioned nicotinate aqueous solution under constantly stirring, finish, adjusting pH is 4-6, preferred pH ≈ 5 promptly has blueness or blue-greenish colour precipitation to separate out.After still aging for some time, centrifugal or suction filtration gets the blue-greenish colour precipitation.Precipitation is washed more than 3 times with water all centrifugal at every turn or suction filtration.To be deposited under 105 ℃ of temperature and be drying to obtain product.
Quality of material proportioning described in the present invention is as follows:
Nicotinic acid: solid alkali metal carbonate: the inorganic mantoquita of solid, water soluble (in copper)=3.9～4.2: 0.93～1.2: 1;
Nicotinic acid: solid alkali metal oxyhydroxide: the inorganic mantoquita of solid, water soluble (in copper)=3.9～4.2: 1.26～1.77: 1.
Solid alkali metal carbonate described in the present invention or supercarbonate are meant soluble carbon hydrochlorate and supercarbonate, as yellow soda ash, sodium bicarbonate, salt of wormwood etc.; Solid alkali metal oxyhydroxide is meant as sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
Catalyzer preferably sulfuric acid nickel described in the present invention, single nickel salt typically refers to NiSO
46H
2O, employed amount is 0.05-0.2% by weight percentage.
Advantage of the present invention is: is reaction medium reaction system at normal temperatures and pressures because preparation technology of the present invention is employing with water.Speed of response is fast, and is with short production cycle, and technology is simpler, reduced investment, and easy to operate without organic reagent thereby cleanliness without any pollution, cost is lower, yield height (＞97%) when adding catalyzer, purity height (＞96%); When not adding catalyzer, yield is not less than 90%, and purity is higher than 93%.The synthetic product is stable, and is quality controllable, bioavailability height, residual Cu in the ight soil
2+Ion seldom discharges to behind the environment, and environmental pollution is few; Just can reach the promotes growth effect of the copper in the original used higher dosage copper sulfate source of field of fodder than the copper in low dosage copper nicotinate source, reduce the wasting of resources, environment for use is polluted and is lacked simultaneously.Because copper nicotinate is more stable, the Cu of unbound state
2+Ion seldom, just be difficult for the catalysis VITAMIN and decompose, also few relatively to the destruction of VITAMIN, in feed processing and storage process, just can directly mix, improve feed processing and storage cost, the inventive method produce product---copper nicotinate is a kind of good fodder additives.
Embodiment:
The present invention is described in detail below in conjunction with implementation column:
Embodiment 1
With 125.5 gram CuSO
45H
2O is dissolved in the water of 500ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 123.1 grams, moistening with 500ml distilled water, slowly add yellow soda ash 60 grams, the limit edged stirs, and this process is emerged with a large amount of bubbles, and after nicotinic acid dissolved fully, the single nickel salt that adds 1 gram was again made catalyzer, stirs.Slowly add the copper-bath of above-mentioned preparation afterwards again, transferring pH with 1: 1 hydrochloric acid soln is 5, still aging 12h, and suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 97.3%, purity 97%.
Embodiment 2
With 250 gram CuSO
45H
2The O powder is dissolved in the water of 1000ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 246 grams, moistening with 1000ml distilled water, slowly add sodium hydroxide 80 grams, the limit edged stirs, to nicotinic acid complete molten after, the single nickel salts that add 1.5 grams are again made catalyzer, stir.Afterwards, slowly add the copper-bath of above-mentioned preparation, finish, transferring pH with 1: 1 hydrochloric acid soln is 5, still aging 12h, and suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 98.3%, purity 97.5%.
Embodiment 3
With 125.5 gram CuSO
45H
2O is dissolved in the water of 500ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 123.1 grams, moistening with 500ml distilled water, slowly add sodium bicarbonate 84 grams, the limit edged stirs, and this process is emerged with a large amount of bubbles, and after nicotinic acid dissolved fully, the single nickel salt that adds 2 grams was again made catalyzer, stirs.Slowly add the copper-bath of above-mentioned preparation afterwards again, finish, transferring pH with the hydrochloric acid soln of 0.1M is 5, still aging 12h, and suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 97.8%, purity 98%.
Embodiment 4
With 250 gram CuSO
45H
2The O powder is dissolved in the water of 1000ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 246 grams, moistening with 1000ml distilled water, slowly add sodium hydroxide 80 grams, the limit edged stirs, to nicotinic acid complete molten after, the single nickel salts that add 1.5 grams are again made catalyzer, stir.Afterwards, slowly add the copper-bath of above-mentioned preparation, finish, transferring pH with the hydrochloric acid soln of 0.1M is 4.0～4.5, still aging 12h, and suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 98.1%, purity 97.8%.
Embodiment 5
With 250 gram CuSO
45H
2The O powder is dissolved in the water of 1000ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 246 grams, moistening with 1000ml distilled water, slowly add potassium hydroxide 112.2 grams, the limit edged stirs, to nicotinic acid complete molten after, the single nickel salt that adds 0.5 gram is again made catalyzer, stirs.Afterwards, slowly add the copper-bath of above-mentioned preparation, finish, transferring pH with the hydrochloric acid soln of 0.1M is 6, still aging 12h, and suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 97.1%, purity 96.8%.
Embodiment 6
With 125.5 gram CuSO
45H
2O is dissolved in the distilled water of 500ml amount and makes copper sulfate solution, and is standby; Claim nicotinic acid 123.1 grams, moistening with 500ml distilled water, slowly add yellow soda ash 60 grams, the limit edged stirs, and this process is emerged with a large amount of bubbles, after nicotinic acid is molten entirely, slowly be added dropwise to the copper-bath of above-mentioned preparation again, the about 2.5h of dropping process finishes, transferring pH with 1: 1 hydrochloric acid soln is 5, continues stirring reaction 3.5h.Still aging 12h, suction filtration gets blue precipitation, uses distilled water wash 3 times, suction filtration, 105 ℃ of dryings promptly get sample.Yield 91.2%, purity 93.6%.
From above embodiment as can be known: finished in the general 20-40 of embodiment 1-5 minute, reaction can be finished; Embodiment 6 dropping processes need 2.5h approximately, finish, and behind the accent pH, continue stirring reaction 3.5h.Thereby embodiment 6 is in that not add the catalyzer following reaction times of condition more of a specified duration, and yield, purity do not have the height of the interpolation catalyzer of embodiment 1-5 yet.
The foregoing description product is analyzed, and the result is as follows:
The results of elemental analyses of embodiment product---title complex sees Table 1, and the result can find out from table: the part of sample A is-Nic its title complex and Cu (Nic)
2Each element theory content conforms in the molecular formula.
The ultimate analysis of table 1. title complex
| Compund | N | C | H | Cu |
| Sample A(Cu(Nic) 2) | 9.02(9.10 *) | 46.53(46.83 *) | 278(262 *) | 21.13(20.65 *) |
*The date in brackets are the calculated values。
The main infrared spectrum absorpting peak data of embodiment product---title complex see Table 2.From table 2 data as can be known, title complex not only the flexible absorption peak of C=O very big red shift takes place; O-H stretching vibration absorption peak all disappears on the nicotinic acid carboxylic acid, this and carboxyl oxygen coordination, H
+Ionic dissociation goes out relevant.Secondly blue red shift has taken place in each interatomic vibration absorption peak on the title complex pyridine ring, meets pyridine nitrogen coordinate feature.
The infrared spectra of table 2. title complex and part
| compound | υ -o＝o | υ -OH | υ C＝N | υ C＝C | υ C-N | υ C-H |
| Hnic Sample A | 1705 1650 | 2817.9，2448. 1 | 1595，1578， 1569，1424 | 1629 1601 | 810，750 851，760 | 1136，1114，1086，1025 1155，1117，1095，1044 |
Embodiment product---title complex is measured through the X-diffraction, by the contrast of standard spectrogram and match of structure cell lattice parameter such as table 3.The lattice parameter data can tentatively be inferred and know sample (Cu (Nic) from table 3
2) cell configuration have two kinds, be monocline rectangular parallelepiped crystallographic system basically, this may be asymmetric relevant with two aglucon size and location in the part.
Table 3Cu (Nic)
2And Cu (Inic)
2The crystal lattices parameter
| Ref. Code | Compound Name | Chemical Formula | Lattice Parameters | |||||
| Bond Lengths(nm) | Bond Angles(°) | |||||||
| a | b | c | α | β | γ | |||
| 21-1601 11-0927 | Copper nicotinate Copper nicotinate | Cu(Nic) 2 Cu(Nic) 2 | 1.26 1.28 | 1.11 0.68 | 0.70 1.16 | 95.2 90 | 89.1 117.9 | 132 2 90 |
Product purity is all greater than 93% by analysis, and the product yield reaches more than 91%, and product is stable, and is quality controllable, reduced investment, technology cleanliness without any pollution.Product bioavailability height; low in the pollution of the environment; less relatively etc. to the destruction of VITAMIN; and the promotes growth effect that just can reach the copper in higher dosage copper sulfate source than the copper in low dosage copper nicotinate source; also can hang down limit environment is polluted simultaneously; and well protected the VITAMIN in the feed, reduced the wasting of resources.It is a kind of good fodder additives.
Claims (8)
1, a kind of preparation method of copper nicotinate comprises the steps:
(1) in reactor, adds formula ratio nicotinic acid and an amount of water, under constantly stirring, slowly add the water-soluble alkaline material of proportional quantity, all be converted into salt and be dissolved into the aqueous solution up to nicotinic acid;
(2) the water-soluble inorganic mantoquita is dissolved in an amount of water after, this aqueous solution is slowly being splashed in the above-mentioned nicotinate aqueous solution under constantly stirring, adjustings pH is 4-6, promptly has blueness or blue-greenish colour to precipitate and separates out; After still aging, centrifugal or suction filtration gets the blue-greenish colour precipitation; Wash with water, behind the centrifugal or suction filtration, drying precipitate is promptly got product.
2, the preparation method of copper nicotinate according to claim 1, it is characterized in that described water-soluble alkaline material comprises alkaline carbonate or supercarbonate or alkali metal hydroxide, the quality proportioning of nicotinic acid and alkaline carbonate and water-soluble inorganic mantoquita is: nicotinic acid: solid alkali metal carbonate: the inorganic mantoquita of solid, water soluble is in copper=3.9～4.2: 0.93～1.2: 1;
The quality proportioning of nicotinic acid and alkali metal hydroxide and water-soluble inorganic mantoquita is: nicotinic acid: solid alkali metal oxyhydroxide: the inorganic mantoquita of solid, water soluble is in copper=3.9～4.2: 1.26～1.77: 1.
3, the preparation method of copper nicotinate according to claim 1 and 2 is characterized in that the water-soluble alkaline material has a kind of yellow soda ash, sodium bicarbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or lithium hydroxide of being selected from least.
4, the preparation method of copper nicotinate according to claim 1 and 2 is characterized in that the water-soluble inorganic mantoquita has a kind of copper sulfate, cupric chloride, cupric nitrate of being selected from least.
5, according to claim 1 or the 2 said methods that prepare copper nicotinate, it is characterized in that in the nicotinate aqueous solution of step (1), adding the transition metal water-soluble salt catalyzer of catalytic amount, carry out step (2) operation again.
6,, it is characterized in that the pH in the step (2) is preferably 5 according to the said method for preparing copper nicotinate of claim 1.
7, according to the said method for preparing copper nicotinate of claim 2, it is characterized in that the quality proportioning of nicotinic acid and alkaline carbonate and water-soluble inorganic mantoquita is: nicotinic acid: yellow soda ash or salt of wormwood: the inorganic mantoquita of solid, water soluble is in copper=3.9～4.2: 0.93～1.2: 1;
The quality proportioning of nicotinic acid and alkali metal hydroxide and water-soluble inorganic mantoquita is: nicotinic acid: sodium hydroxide or potassium hydroxide: the inorganic mantoquita of solid, water soluble is in copper=3.9～4.2: 1.26～1.77: 1.
8,, it is characterized in that described transition metal water-soluble salt catalyzer preferably sulfuric acid nickel according to the said method for preparing copper nicotinate of claim 5.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817495A (en) * | 2015-04-29 | 2015-08-05 | 哈尔滨师范大学 | Production method and application of copper-cone-shaped copper nicotinate micron materials |
| WO2016037181A1 (en) * | 2014-09-06 | 2016-03-10 | C Lab Pharma International, S.A. | Pure chelation process |
| CN106000279A (en) * | 2016-06-27 | 2016-10-12 | 温州大学 | Nano-nickel oxide with adsorptivity and preparation method of nano-nickel oxide |
| RU2647072C1 (en) * | 2017-06-08 | 2018-03-13 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method for obtaining coordination compound of copper(ii) with nicotinic acid |
-
2006
- 2006-09-30 CN CN 200610124693 patent/CN1931844A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037181A1 (en) * | 2014-09-06 | 2016-03-10 | C Lab Pharma International, S.A. | Pure chelation process |
| EP3188835A4 (en) * | 2014-09-06 | 2018-05-09 | C Lab Pharma International, S.A. | Pure chelation process |
| US10258980B2 (en) | 2014-09-06 | 2019-04-16 | C Lab Pharma International, S.A. | Pure chelation process |
| CN104817495A (en) * | 2015-04-29 | 2015-08-05 | 哈尔滨师范大学 | Production method and application of copper-cone-shaped copper nicotinate micron materials |
| CN104817495B (en) * | 2015-04-29 | 2017-05-24 | 哈尔滨师范大学 | Production method and application of copper-cone-shaped copper nicotinate micron materials |
| CN106000279A (en) * | 2016-06-27 | 2016-10-12 | 温州大学 | Nano-nickel oxide with adsorptivity and preparation method of nano-nickel oxide |
| CN106000279B (en) * | 2016-06-27 | 2018-09-04 | 温州大学 | A kind of nano-nickel oxide and preparation method thereof with adsorptivity |
| RU2647072C1 (en) * | 2017-06-08 | 2018-03-13 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method for obtaining coordination compound of copper(ii) with nicotinic acid |
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