CN101318929B - Synthesis process for chromium picolinate - Google Patents
Synthesis process for chromium picolinate Download PDFInfo
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- CN101318929B CN101318929B CN2008100629319A CN200810062931A CN101318929B CN 101318929 B CN101318929 B CN 101318929B CN 2008100629319 A CN2008100629319 A CN 2008100629319A CN 200810062931 A CN200810062931 A CN 200810062931A CN 101318929 B CN101318929 B CN 101318929B
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- chromium picolinate
- picolinate
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Abstract
The invention discloses a process for synthesizing chromium picolinate. The process uses 2-pyridinecarbonitrile and chromic salt as reactants to generate the chromium picolinate by one-step hydro-thermal synthesis reaction at a temperature of between 80 and 200 DEG C under 2 to 3 standard atmospheric pressure. The process has simple operation, easily realizes mass production, and greatly reduces the manufacturing cost; moreover, the whole process is a green production with low environmental pollution.
Description
Technical field
The present invention relates to the synthesis technique of chromium picolinate (2-chromium picolinate).
Background technology
Chromium (Cr) is a kind of important nutritive ingredient, and the major physiological effect of chromium is to influence carbohydrate, the proteinic metabolism of lipid machine by strengthening insulin function.Studies have shown that in recent years, in animal high strength vegetative period, chromium not only can be regulated protein metabolism, but also can be used as health and the growth performance that immunomodulator influences animal, in the appetite structure of China, because refining, processing and soil is by drip washing, the intake of chromium seldom.Therefore, no matter be that the mankind or animal generally all lack chromium, this effect can be easy to find out from the favourable reaction of animal throughput behind the benefit chromium, we can say that therefore chrome content is all not enough in the used daily ration of herding production, and the supply of chromium should be mentioned that on the schedule.
Chromic salts generally is divided into trivalent chromium and sexavalence chromic salts, and sexavalent chrome toxicity is big, and trivalent chromium toxicity is less, but under present feed rules condition, it is unallowed adding inorganic chromium in animal and fowl fodder.And the chromic salt of pyridine carboxylic acid is nontoxic, can be used for the interpolation of feed.In the chromic salt of pyrrole heavy stone used as an anchor formic acid, 2-chromium picolinate (also claim chromium picolinate, be commonly called as organic chromium) is important feed and the foodstuff additive of a class that development in recent years is got up, and use is widely especially arranged aspect fodder industry.The synthesis technique of 2-chromium picolinate has multiple at present, but its basic synthesis step all is to adopt 2-pyridine carboxylic acid and chromic salt reaction Synthetic 2-chromium picolinate, a kind of synthetic method of 2-chromium picolinate is disclosed as Chinese invention patent application number 200510012886.2, it gets the 2-pyridine carboxylic acid by the 2-picoline through oxidizing reaction earlier, and the 2-pyridine carboxylic acid reacts Synthetic 2-chromium picolinate with chromic salts more then.Chinese invention patent application number 01141486.3 open fodder additives 2-chromium picolinate synthesis technique, its building-up process is to get the 2-pyridine carboxylic acid by the 2-vinyl pyridine through oxidizing reaction, the 2-pyridine carboxylic acid promptly gets the 2-chromium picolinate with the chromic salts reaction more then.Above-mentioned two kinds of synthesis techniques, step is many, operation easier is big and exist oxygenant to reclaim problem, causes environmental pollution easily.U.S. Patent number 5677461 discloses the chromium picolinate synthesis technique, it obtains the 2-chromium picolinate by 2-pyridine carboxylic acid and chromic salts reaction, directly generate the technology of chromium picolinate by 2-pyridine carboxylic acid and chromic salts generation complex reaction, because the 2-pyridine carboxylic acid costs an arm and a leg, holding at high price of the feasible 2-chromium picolinate of producing directly has influence on 2-chromium picolinate applying in fodder additives and foodstuff additive.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and a kind of simple to operate, cost is low, few chromium picolinate is polluted in reaction synthesis technique is provided.
For achieving the above object, technical scheme of the present invention is, uses 2-cyanopyridine and water-soluble chromic salt to be reactant, generates chromium picolinate by one step of hydrothermal synthesis reaction under 80-200 ℃, a 2-3 standard atmosphere pressure, and its reaction formula is:
Reaction after product chromium picolinate solubleness in water is very low, can crystallize out, and filters promptly separable, remaining have only ammonia salt, because reaction system is airtight, remaining ammonia salt can not produce the ammonia contaminate environment, and ammonia salt can obtain the crystallization of ammonia salt as byproduct after concentrating.Whole technology is polluted few, and the atom utilization height meets the notion and the requirement of Green Chemistry.
Through synthetic product of the present invention is the purple crystallite, also can cultivate into big crystal, resolves through the X ray single crystal diffraction, proved this structure, this structure and a water molecules cocrystallization are separated out, and are connected by hydrogen bond, form an one-dimensional chain structure (Fig. 1, shown in Figure 2)
Product turns out to be 2-Pyridinecarboxylic Acid chromium through ultimate analysis in addition
Carbon wherein, hydrogen and nitrogen are measured with EA 1112 type elemental analysers; IR measures (KBr compressing tablet) with EQUINOX55 type infrared spectrometer (Bruker company); MS measures with 1100LC/MSD TrapSL type liquid chromatograph/mass spectrometer, and the monocrystalline data are measured by Mercury CCD single crystal diffractometer, obtain following data:
The ultimate analysis data, calculated value %:C 51.68, H 2.87, and N 10.05; Measured value %:C 51.88, H 2.79, and N 10.07.
IR, ν
Max(cm
-1): 3048 (W, C-H), 1677 (S, C=O unsymmetrically), 1619 (m, C=C, C=N), 1325 (S, C=O symmetries).
MS(M/Z)：419(M
+，15％)
Product is a 2-Pyridinecarboxylic Acid chromium as can be known.
Further being provided with is that described water-soluble chromic salt is chromium trichloride, chromium nitrate, chromium sulphate.
Further being provided with is that above-mentioned reaction process is to carry out in the autoclave that is liner with the tetrafluoroethylene.
The invention has the advantages that:
1, simple to operate, be easy to accomplish scale production, the present invention need not to add any reagent, produce under pressure and the heating condition by water vapor, directly the 2-cyanopyridine is oxidized to the 2-pyridine carboxylic acid, the 2-pyridine carboxylic acid generates the 2-chromium picolinate with the chromium complexing again, two-step reaction carries out simultaneously, directly generated the 2-chromium picolinate, entire operation can directly be carried out in autoclave, and is simple to operate;
2, greatly reduced production cost, the about 140,000/ton of the present commercially available price of reactant 2-cyanopyridine that the present invention adopts, market price far below the about 400,000/ton of 2-pyridine carboxylic acid, and the present invention only adds 2-chromium picolinate and ammonia salt in synthetic, side reaction is few, impurity is few, and product is easy to separate product productive rate height;
3, reaction is enclosed system, and entire reaction produces to be polluted less and may command, can realize green production, reduces environmental pollution.
Figure of description
The crystal X ray single crystal diffraction synoptic diagram of Fig. 1 synthetic product of the present invention
The crystal X ray single crystal diffraction accumulation graph of Fig. 2 synthetic product of the present invention
Embodiment
Embodiment 1
2-cyanopyridine and chromium trichloride join with in the teflon-lined 30ml autoclave according to mol ratio at 3: 1, the water that adds about 20ml, reactor is tightened post-heating to 150 degree, under 2-3 standard atmosphere pressure, kept 150 degree constant temperature 24 hours, generate pink chromium picolinate, productive rate is 96.2%.
Embodiment 2:
2-cyanopyridine and chromium trichloride join with in the teflon-lined 30ml autoclave according to mol ratio at 3: 1, the water that adds about 15ml, reactor is tightened post-heating to 100 degree, kept 100 degree constant temperature about 2 standard atmosphere pressures 24 hours, generate pink chromium picolinate, productive rate is 95.6%.
Embodiment 3:
2-cyanopyridine and chromium trichloride join with in the teflon-lined 30ml autoclave according to mol ratio at 3: 1, the water that adds about 20ml, reactor is tightened post-heating to 80 degree, kept 80 degree constant temperature about 2 standard atmosphere pressures 48 hours, generate chromium picolinate, productive rate is 96.5%.This synthesis technique productive rate is the highest, can be used as preferred embodiment of the present invention.
Claims (3)
1. the synthesis technique of a chromium picolinate, it is characterized in that: use 2-cyanopyridine and water-soluble chromic salt to be reactant, generate chromium picolinate by a step hydrothermal synthesis reaction under 80-200 ℃, a 2-3 standard atmosphere pressure, its reactive chemistry equation is:
2. the synthesis technique of chromium picolinate according to claim 1, it is characterized in that: described water-soluble chromic salt is chromium trichloride, chromium nitrate, chromium sulphate.
3. the synthesis technique of chromium picolinate according to claim 1 and 2, it is characterized in that: above-mentioned reaction process is to carry out in the autoclave that is liner with the tetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2008100629319A CN101318929B (en) | 2008-07-04 | 2008-07-04 | Synthesis process for chromium picolinate |
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| CN2008100629319A CN101318929B (en) | 2008-07-04 | 2008-07-04 | Synthesis process for chromium picolinate |
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| CN101318929A CN101318929A (en) | 2008-12-10 |
| CN101318929B true CN101318929B (en) | 2010-08-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602716B (en) * | 2009-04-29 | 2011-05-25 | 南通醋酸化工股份有限公司 | Synthesis method of 2-chromium picolinate |
| CN103319401A (en) * | 2013-05-22 | 2013-09-25 | 中牧实业股份有限公司 | Technology for preparing 2-chromium picolinate through one-step method |
| CN107333975B (en) * | 2017-08-14 | 2019-10-08 | 淄博职业学院 | A kind of novel processing step of chromium picolinate based food additive |
| CN107337638A (en) * | 2017-08-14 | 2017-11-10 | 侯茜茜 | A kind of high-efficiency synthesis method of pyridine carboxylic acid based food additive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5677461A (en) * | 1995-04-13 | 1997-10-14 | Republic Of Korea Represented By Rural Development Administration | Method for producing chromium picolinate complex |
| CN1408708A (en) * | 2001-09-27 | 2003-04-09 | 张敏红 | Process for synthesizing 2-pyridine chromium formate of fodder additive |
| CN1772737A (en) * | 2005-09-30 | 2006-05-17 | 中国科学院山西煤炭化学研究所 | Synthesis process of chronium 2-picolinate |
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2008
- 2008-07-04 CN CN2008100629319A patent/CN101318929B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5677461A (en) * | 1995-04-13 | 1997-10-14 | Republic Of Korea Represented By Rural Development Administration | Method for producing chromium picolinate complex |
| CN1408708A (en) * | 2001-09-27 | 2003-04-09 | 张敏红 | Process for synthesizing 2-pyridine chromium formate of fodder additive |
| CN1772737A (en) * | 2005-09-30 | 2006-05-17 | 中国科学院山西煤炭化学研究所 | Synthesis process of chronium 2-picolinate |
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