KR0184380B1 - Method for preparing picoline acid chronium - Google Patents
Method for preparing picoline acid chronium Download PDFInfo
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- KR0184380B1 KR0184380B1 KR1019950051991A KR19950051991A KR0184380B1 KR 0184380 B1 KR0184380 B1 KR 0184380B1 KR 1019950051991 A KR1019950051991 A KR 1019950051991A KR 19950051991 A KR19950051991 A KR 19950051991A KR 0184380 B1 KR0184380 B1 KR 0184380B1
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- Prior art keywords
- chromium
- acid
- reaction
- minutes
- picolinate
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- 239000002253 acid Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 12
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011651 chromium Substances 0.000 claims abstract description 25
- 229940081066 picolinic acid Drugs 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229940046374 chromium picolinate Drugs 0.000 claims description 15
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 241001465754 Metazoa Species 0.000 abstract description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 9
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 102000004877 Insulin Human genes 0.000 description 3
- 108090001061 Insulin Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229940125396 insulin Drugs 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- -1 picolinate chromium Chemical compound 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OBLMZHIGRDQQFJ-UHFFFAOYSA-L N1=C(C=CC=C1)C(=O)O.[Cr](=O)(=O)(O)O Chemical compound N1=C(C=CC=C1)C(=O)O.[Cr](=O)(=O)(O)O OBLMZHIGRDQQFJ-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2200/00—Function of food ingredients
- A23V2200/30—Foods, ingredients or supplements having a functional effect on health
- A23V2200/328—Foods, ingredients or supplements having a functional effect on health having effect on glycaemic control and diabetes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2250/00—Food ingredients
- A23V2250/30—Other Organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
본 발명에 따라 식품 또는 동물 사료의 첨가제로서 사용되는 고순도 피콜린산크롬을 고수율로 얻을 수 있는 새로운 제조방법이 제공된다. 본 발명의 방법은 +3가 크롬의 강산염과, 동 당량의 피콜린산을 물에 녹여 70-100℃에서 20분 이상 가열한 후 이 반응에서 생성될 수 있는 산의 전량을 중화시키는데 필요한 알칼리의 50-100%를 반응액의 pH가 3.5 이하가 되도록 유지하면서 반응액에 가한 후 계속 70-100℃에서 20분 이상 가열하는 것으로 이루어진다.According to the present invention, there is provided a new production method capable of obtaining in high yield chromium high purity picolinate used as an additive in food or animal feed. The method of the present invention is a strong acid of + trivalent chromium and an alkali equivalent required to neutralize the total amount of acid that can be produced in this reaction after dissolving the same amount of picolinic acid in water and heating it at 70-100 ° C for at least 20 minutes. 50-100% of the solution was added to the reaction solution while maintaining the pH of the reaction solution below 3.5, followed by heating at 70-100 ° C. for at least 20 minutes.
Description
본 발명은 피콜린산크롬의 제조방법에 관한 것이다. 더욱 구체적으로는 식품 및 동물 사료에 첨가되는 고순도 피콜린산크롬을 고수율로 제조할 수 있는 새로운 제조방법에 관한 것이다.The present invention relates to a process for the preparation of chromium picolinate. More specifically, the present invention relates to a new production method capable of producing high purity chromic choline phosphate added to food and animal feed in high yield.
크롬을 포함하는 유기물은 체내의 인슐린 작용을 최적화하는데 있어서 필수적인 성분이라는 것이 밝혀졌고 (K. Schwarz 및 W. Mertz, Arch Biochem. Biophys., 85, 292 (1959)), 특히 피콜린산크롬은 글루코스 내성인자 (GTF)의 주요성분으로서 글루코스의 분해작용 및 글루코스의 지방 전환을 위한 인슐린 작용에 직접 관여한다는 사실이 알려졌다 (W. Mertz 외, Nutrition Review 25, 49 (1967)). 더욱이, 최근에는 여러가지 동물 및 인체 인상실험을 통하여 피콜린산크롬이 인슐린 대사에 관여하여 체내의 혈당을 낮추고, 콜레스테롤 및 체지방을 감소시키는 한편 근육질을 강화한다는 연구결과 (G. W. Evans, Int. J. Biosocial Med. Research, 11(2), 163 (1989))가 발표되었으며, 돼지 사료에 피콜린산크롬을 200ppb 정도로 첨가하여 사육할 경우, 돼지의 지방질과 콜레스테롤 수준은 낮아지고 근육질 함량은 증가한다는 사실 등이 보고되고 있다 (K. Jacques 외, Feed Management, 44, 23 (1993)).Organic matter containing chromium has been found to be an essential ingredient in optimizing insulin action in the body (K. Schwarz and W. Mertz, Arch Biochem. Biophys., 85, 292 (1959)), in particular chromium phycocholine is glucose It is known that it is directly involved in the degradation of glucose and the action of insulin for fat conversion of glucose as a major component of resistance factor (GTF) (W. Mertz et al., Nutrition Review 25, 49 (1967)). Furthermore, recent studies on animal and human impressions have shown that phycocholic acid chromium is involved in insulin metabolism, lowering blood sugar in the body, reducing cholesterol and body fat, and strengthening muscle (GW Evans, Int. J. Biosocial Med. Research, 11 (2), 163 (1989)) reported that breeding with 200 ppb of picolinate in pig feed lowered the fat and cholesterol levels of pigs and increased muscle content. (K. Jacques et al., Feed Management, 44, 23 (1993)).
이러한 식품 및 동물 사료 첨가용 피콜린산크롬은 고순도일 것과 식품 또는 동물 사료에 첨가 및 배합하기에 용이한 형태일 것이 요구되며, 아울러 그 제조방법은 수율이 높고 부산물이 적은 공정이라야 한다. 그러나, 종래 기술상의 문헌에 보고된 피콜린산크롬의 제조방법은 의외로 그 수가 많지 않고 그나마 출발물질의 종류에 따라 사용 용매, 반응 온도, 반응 시간 등 반응 조건이 너무 판이하고, 수율도 50-70%로 비교적 낮은 것으로 보고되어 있다. 예컨대, 질산크롬(Cr(NO3)3·9H2O)과 피콜린산을 반응시키는 경우 (D. M. Stearns 외, Inorg. Chem., 31, 5178 (1992)), 질산크롬과 피콜린산을 질산 수용액에 녹여 60℃에서 30분간 가열한 후 식히면 약 48%의 수율로 피콜린산크롬이 얻어지는 것으로 보고되어 있다. 또한, 아세트산 크롬(Cr(OOCCH3)3·H2O)과 피콜리산을 역시 수용액에서 가열 반응시킬 경우 (A. J. Saraceno, Inorg. Chem. 2, 865 (1963)), 피콜린산크롬이 약 70%의 수율로 얻어지는 것으로 설명되어 있다. 한편, G. W. Evans는 염화크룸 (CrCl3·6H2O)과 피콜린산을 1 : 3의 몰비로 수용액에서 반응시키면 상온에서는 1시간, 37℃에서는 10분 가열하면 반응이 완결된다고 보고하고 있으나 (G. W. Evans, 외, J. Inorg. Biochem., 49,177 (1993)), 이 반응 조건에서의 실제 수율은 50% 미만이다. 이외에도 삼염화크롬과 피콜린산을 알코올 용매에서 반응시키는 방법 (G. Yuen 외, Inorg. Chim. Acta., 73, 231 (1983)), 헥사카르보닐크롬과 피콜린산을 메탄올 용매에서 반응시키는 방법 (T. E. Dorsett 외, J. Chem. Soc. Dalton, 347 (1976)) 등이 보고되어 있으나, 황산크롬 (Cr(SO4)3xH2O)을 출발물질로 사용하는 방법은 전혀 보고되고 있지 않다.Such chromic acid picolinate for food and animal feed is required to be of high purity and easy to add and blend into food or animal feed, and the production method should be a process with high yield and low by-products. However, the manufacturing method of chromium picolinate reported in the prior art literature is not surprisingly large, and depending on the kind of starting material, the reaction conditions such as solvent, reaction temperature, reaction time, and the like are very different, and the yield is 50-70. It is reported to be relatively low in%. For example, when chromium nitrate (Cr (NO 3 ) 3 .9H 2 O) is reacted with picolinic acid (DM Stearns et al., Inorg. Chem., 31, 5178 (1992)), chromium nitrate and picolinic acid It is reported that chromium picolinate is obtained by dissolving in an aqueous solution, heating at 60 ° C. for 30 minutes, and cooling it in a yield of about 48%. In addition, when chromium acetate (Cr (OOCCH 3 ) 3 H 2 O) and picolinic acid are also heated in an aqueous solution (AJ Saraceno, Inorg. Chem. 2, 865 (1963)), chromium picolinate is weak. It is described as being obtained in a yield of 70%. On the other hand, GW Evans reports that kCl chloride (CrCl 3 · 6H 2 O) and picolinic acid are reacted in an aqueous solution at a molar ratio of 1: 3, and the reaction is completed when heated for 1 hour at room temperature and 10 minutes at 37 ° C. GW Evans, et al., J. Inorg. Biochem., 49,177 (1993)), the actual yield at these reaction conditions is less than 50%. In addition, a method of reacting chromium trichloride and picolinic acid in an alcohol solvent (G. Yuen et al., Inorg. Chim. Acta., 73, 231 (1983)), and a method of reacting hexacarbonylchromium and picolinic acid in a methanol solvent (TE Dorsett et al., J. Chem. Soc. Dalton, 347 (1976)) and the like have been reported, but no method of using chromium sulfate (Cr (SO 4 ) 3 x H 2 O) as a starting material at all. .
상술한 크롬의 산성염과 피콜린산의 반응은 일견 간단해 보이지만, 반응 조건에 따라 킬레이션 된 착화합물형태의 피콜린산크롬 (Cr(pic)3H2O)The reaction of the acid salt of chromium and picolinic acid described above may seem simple, but chromium picolinate in the form of a complex compound chelated according to the reaction conditions (Cr (pic) 3 H 2 O)
즉외에 이합체인 [Cr(pic)2(OH)]2또는 킬레이트 화합물이 아닌 크롬과 피콜린산과의 단순한 수용성 이온 화합물인등의 불순물이 공침하게 됨에 따라 제품 수율이 낮아지는 것으로 추정된다.In other words In addition to dimers [Cr (pic) 2 (OH)] 2 or chelating compounds, it is a simple water-soluble ionic compound of chromium and picolinic acid. As the impurities such as coprecipitate, the product yield is estimated to decrease.
따라서, 본 발명의 목적은 식품 및 동물 사료에 첨가되기 위한 피콜린산크롬을 고순도(99%)로, 정량적으로 제조하기 위한 새로운 방법을 제공하는 데 있다. 본 발명자들은 종래기술에 따른 방법들을 면밀히 검토, 실험한 결과, 출발물질에 거의 관계없이 순도 99.0% 이상의 고순도 결정성 피콜린산크롬을 99% 이상의 고수율로 제조할 수 있는 공정을 발견하기에 이르렀다.Accordingly, it is an object of the present invention to provide a new method for the quantitative preparation of chromic picolinate for high purity (99%) for addition to food and animal feed. As a result of careful examination and experimentation of the methods according to the prior art, the present inventors have found a process capable of producing high purity crystalline picolinate chromium with a purity of 99.0% or more with a high yield of 99% or more regardless of starting materials. .
본 발명에 따른 피콜린산크롬의 새로운 제조방법을 상세히 설명하면 다음과 같다.Referring to the new manufacturing method of chromium picolinate according to the present invention in detail.
본 발명에 따른 신 공정의 핵심내용을 설명하면, 우선 종래 기술에 따른 반응 온도는 모두 60℃ 이하였던데 비하여, 본 발명에서는 70-100℃의 상승된 온도에서 반응을 진행시키는데, 이것은 후술되는 바와 같이 종래 기술에 비교하여 큰 의미를 갖는 것이다. 즉, 본 발명자들은 종래 기술에서와 같은 60℃ 이하의 반응 온도 범위에서는 앞의 구조식에서와 같이 피콜린산이 크롬 금속과 킬레이션하여 안정한 착화합물을 형성하는데 충분치 못함을 발견하게 되었다. 즉, 70-100℃에서 10분 -30분 이상 가열하여야만 착화합물의 형성 반응이 용이하게 진행된다는 사실이 본 발명자들에 의해 밝혀졌다. 다시 말하면, 낮은 온도에서는 다음 반응식 (I):Referring to the core of the new process according to the present invention, first, the reaction temperature according to the prior art was all 60 ℃ or less, in the present invention, the reaction proceeds at an elevated temperature of 70-100 ℃, which will be described later Likewise, it has a great meaning compared with the prior art. That is, the inventors have found that in the reaction temperature range of 60 ° C. or lower as in the prior art, the picolinic acid is not sufficient to chelate with the chromium metal to form a stable complex as in the above structural formula. That is, it was found by the present inventors that the formation reaction of the complex compound proceeds easily only after heating at 70-100 ° C. for 10 minutes to 30 minutes or more. In other words, at low temperatures the following reaction (I):
에서와 같은 킬레이션 반응이 잘 일어나지 않고, 대부분 단순한 카르복실산염, 즉,이 형성되며, 70℃ 이상으로 가열하여야 킬레이션 반응이 순조롭게 일어나 반응식 (I)이 주반응이 되는 것으로 추정된다. 그러나, 상술한 크롬의 산성염과 피콜린산을 70-100℃에서 30분 이상 가열하여도 피콜린산크롬의 수율은 80-90%가 최대였으며 그 이상 반응이 진행되지 않는 것으로 나타났다. 본 발명자들은 그 원인을 면밀히 조사, 분석하여 실험한 결과 반응식(I)이 오른쪽으로 진행하여 생성물인 피콜린산크롬이 침전함에 따라, 반응액의 산도가 급격히 높아져서 pH가 1 이하로 떨어지며, 이러한 강한 산성에서는 아직 확실한 이유를 알 수는 없으나 피콜린산크롬의 생성이 억제되는 것으로 관찰되었다. 따라서, 본 발명자들은 반응식 (I)이 진행되는 중간에 반응식 (I)에서 생성되는 전체산 (HX)의 이론양의 50-100%를 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산칼륨, 산성탄산나트륨, 또는 산성탄산칼륨과 같은 알칼리로 중화하여 pH를 1.5~3.5사이로 유지하면서 반응을 계속시키면 피콜린산크롬을 수율 99% 이상으로, 즉, 거의 정량적으로 얻을 수 있음을 발견하였다.The chelation reaction as in does not occur very well, and mostly simple carboxylates, that is, Is formed, and it is estimated that the heating reaction is smoothly performed at 70 ° C. or higher so that the reaction (I) becomes the main reaction. However, even when the above-described acid salt of chromium and picolinic acid were heated at 70-100 ° C. for 30 minutes or more, the yield of chromium picolinate was 80-90%, and the reaction did not proceed further. The present inventors carefully investigated and analyzed the cause of the experiment, and as a result, the reaction formula (I) proceeded to the right to precipitate the chromium picolinate, so that the acidity of the reaction solution rapidly increased and the pH dropped to 1 or less. In acidic, no clear reason is known, but the production of chromium picolinate was inhibited. Accordingly, the inventors have found that 50-100% of the theoretical amount of the total acid (HX) produced in Scheme (I) in the middle of Scheme (I) is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium carbonate, or It was found that chromium picolinate can be obtained in a yield of 99% or more, ie, almost quantitatively, by continuing the reaction while maintaining the pH between 1.5 and 3.5 by neutralizing with an alkali such as acidic potassium carbonate.
본 발명의 요지를 더욱 상세히 설명하면, 염화크롬, 질산크롬 또는 황산크롬과 같은 +3가 크롬 (Cr(III))의 강산염과, 크롬과 거의 같은 당량의 피콜린산을 가능한 한 최소량의 물에 녹인 후, 서서히 저어주면서 70-100℃에서 20-30분간 1차 가열한 후, 생성될 전체 산 이론양의 50-100%를 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산칼륨, 산성탄산나트륨, 및 산성탄산칼륨과 같은 알칼리로 중화하여 반응액의 pH를 1.5 내지 3.5로 유지하면서 다시 가열 반응을 20-30분간 계속한 후 식히면, 고순도의 피콜린산크롬을 거의 정량적으로 얻을 수 있었다. 상기 중화 반응은 경우에 따라 한번에 하지 않고, 두번 또는 다단계로 나누어 중화하는 것이 더 효과적인 때도 있었다. 그러나, 어떠한 경우에도 반응 용액의 pH가 3.5 이상이 되어서는 절대로 안된다. 왜냐하면, pH=3.5 이상에서는 이합체와 같은 불순물의 생산이 많아지기 때문이다.In more detail, the gist of the present invention is a minimum amount of water containing + trivalent chromium (Cr (III)) strong acid salts such as chromium chloride, chromium nitrate or chromium sulfate, and an equivalent amount of picolinic acid equivalent to chromium. After dissolving in, firstly heated at 70-100 ° C. for 20-30 minutes while stirring slowly, and then 50-100% of the total acid theoretical amount to be produced is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium carbonate, and acidic acid. After neutralizing with an alkali such as potassium carbonate and maintaining the pH of the reaction solution at 1.5 to 3.5, the heating reaction was continued for 20-30 minutes, and then cooled, whereby high purity chromium picolinate could be obtained quantitatively. In some cases, it is more effective to neutralize the neutralization reaction in two or multiple stages rather than in one case. However, in no case should the pH of the reaction solution be more than 3.5. This is because, at pH = 3.5 or more, the production of impurities such as dimers increases.
이와 같이, 종래 기술에 비하여 반응온도를 70-100℃로 높여 피콜린산의 킬레이션을 촉진하고 반응 과정에서 생산되는 산을 중화해 줌으로써 피콜린산크롬의 생성 반응을 완결시키는 본 발명의 방법은, 결정성 고순도 (순도 99.0% 이상)의 피콜린산크롬을 99% 이상의 수율로 거의 정량적으로 얻을 수 있어 경제성이 크게 향상되었다는 것과, 미반응물의 회수가 필요없고, 폐수처리가 아주 용이하여 환경오염이 거의 없다는 장점을 부가적으로 갖는다.As described above, the method of the present invention is completed by increasing the reaction temperature to 70-100 ℃ to promote the chelation of picolinic acid and neutralize the acid produced in the reaction process to complete the production reaction of chromium picolinate , Crystalline high purity (more than 99.0% purity) of chromic picolinate can be obtained almost quantitatively with a yield of 99% or more, which greatly improves economic efficiency, does not require the recovery of unreacted materials, and is very easy to treat wastewater. This additionally has the advantage that there is little.
다음 실시예를 통해 본 발명을 더욱 상세히 설명할 것이나 본 발명이 이들 실시예로 한정되는 것은 아니다.The following examples will further illustrate the present invention, but the present invention is not limited to these examples.
[실시예 1]Example 1
염화크롬 (CrCl36H2O) 5.30g (0.020 mole)과 피콜린산 (PicH) 7.76g (0.063 mole)을 증류수 30ml에 녹인 후 서서히 저으면서 80℃에서 30분간 가열한다. 이 반응에서 생성될 전체 염산의 중화에 필요한 양의 80%에 해당되는 수산화나트륨 1.92g (0.048 mole)을 증류수 4ml에 녹인 수용액을 위 반응액에 반응액의 pH가 3.5 이하로 유지되도록 하면서 서서히 가한 다음, 80℃에서 30분간 계속 반응시킨다. 여기에 다시 수산화나트륨 0.36g (0.009 mole)을 증류수 1ml에 녹인 용액을 pH 3.5이하로 유지하면서 서서히 가한 후 계속 80℃에서 20분간 더 가열한다. 반응액을 식힌 후, 붉은 결정성 침전물을 여과하여 증류수로 2-3회 씻은 후 말리면 8.63g (수율 99.0%)의 피콜린산크롬(Cr(Pic)3H2O)이 얻어진다.5.30 g (0.020 mole) of chromium chloride (CrCl 3 6H 2 O) and 7.76 g (0.063 mole) of picolinic acid (PicH) are dissolved in 30 ml of distilled water, and the mixture is slowly stirred and heated at 80 ° C. for 30 minutes. An aqueous solution of 1.92 g (0.048 mole) of sodium hydroxide, which is 80% of the amount required to neutralize the total hydrochloric acid to be produced in this reaction, was slowly added to the reaction solution while maintaining the pH of the reaction solution at 3.5 or less. Then, the reaction is continued for 30 minutes at 80 ° C. Here again, a solution of 0.36 g (0.009 mole) of sodium hydroxide dissolved in 1 ml of distilled water was slowly added while maintaining the pH at 3.5 or lower, followed by further heating at 80 ° C. for 20 minutes. After cooling the reaction solution, the red crystalline precipitate was filtered, washed 2-3 times with distilled water, and dried to give 8.63 g (yield 99.0%) of picolinate chromium (Cr (Pic) 3 H 2 O).
녹는점: 440℃ (분해)Melting Point: 440 ℃ (Decomposition)
시성식: C18H14N3O7CrAge Formula: C 18 H 14 N 3 O 7 Cr
원소분석치 (%): C, 49.2; H, 3.14; N, 9.39; Cr, 12.0Elemental analysis (%): C, 49.2; H, 3.14; N, 9.39; Cr, 12.0
이론치 (%): C, 49.6; H, 3.23; N, 9.63; Cr, 11.9Theoretical (%): C, 49.6; H, 3. 23; N, 9.63; Cr, 11.9
적외선 흡수띠 (cm-1): 474(s), 658(m), 692(s), 714(s), 766(s), 1030(m), 1050(s), 1096(m), 1152(s), 1238(s), 1260(s), 1288(s), 1326(s), 1352(sh), 1452(m), 1472(s), 1566(m), 1606(s), 1678(vs), 3452(s), 3526(s).Infrared absorption band (cm -1 ): 474 (s), 658 (m), 692 (s), 714 (s), 766 (s), 1030 (m), 1050 (s), 1096 (m), 1152 ( s), 1238 (s), 1260 (s), 1288 (s), 1326 (s), 1352 (sh), 1452 (m), 1472 (s), 1566 (m), 1606 (s), 1678 ( vs), 3452 (s), 3526 (s).
[실시예 2]Example 2
황산크롬 (Cr2(SO4)34H2O) 4.64g (0.010 mole)과 피콜린산 (PicH) 7.76g (0.063 mole)을 증류수 35ml에 녹인 후 서서히 저으면서 80℃에서 30분간 교반한다. 이 반응에서 생성될 전체 황산의 중화에 필요한 양의 50%에 해당되는 수산화나트륨 1.2g (0.030 mole)을 증류수 3ml에 녹인 용액을 위 반응액에 반응액의 pH가 3.5를 넘지 않는 범위에서 서서히 가한 다음 계속 80℃에서 30분간 저어주면 붉은색 결정성 침전이 떨어진다. 용액을 식힌 후 여과하여 증류수로 2-3회 씻은 후 100℃에서 건조기에서 건조하면 8.69g (수율 99.7%)의 피콜린산크롬이 얻어진다.4.64 g (0.010 mole) of chromium sulfate (Cr 2 (SO 4 ) 3 4H 2 O) and 7.76 g (0.063 mole) of picolinic acid (PicH) are dissolved in 35 ml of distilled water, and then stirred at 80 ° C. for 30 minutes while slowly stirring. A solution of 1.2 g (0.030 mole) of sodium hydroxide, which is 50% of the amount required to neutralize the total sulfuric acid to be produced in this reaction, was dissolved in 3 ml of distilled water, and then slowly added to the reaction solution in a range where the pH of the reaction solution did not exceed 3.5. Then continue stirring for 30 minutes at 80 ℃ red crystalline precipitate falls. After cooling, the solution was filtered, washed 2-3 times with distilled water, and dried in a drier at 100 ° C. to obtain 8.69 g (yield 99.7%) of chromic picolinate.
[실시예 3]Example 3
질산크롬 (Cr(NO3)39H2O) 9.04g (0.020 mole)과 피콜린산 (PicH) 8.13g (0.066 mole)을 증류수 40ml에 녹인 후 서서히 저으면서 90℃에서 30분간 교반한다. 여기에 반응시 생성될 전체 질산의 중화에 필요한 양의 90%에 해당되는 수산화나트륨 2.16g (0.054 mole)을 증류수 5ml에 녹인 용액을 반응액의 pH가 3.5를 넘지않도록 서서히 가한 다음 계속 80℃에서 30분간 계속 반응시킨다. 반응액을 식힌 후 생성된 붉은 색 결정성 침전을 걸러 증류수로 2-3회 씻은 다음 건조하면 8.64g (수율 99.1%)의 피콜린산크롬이 얻어진다.9.04 g (0.020 mole) of chromium nitrate (Cr (NO 3 ) 3 9H 2 O) and 8.13 g (0.066 mole) of picolinic acid (PicH) are dissolved in 40 ml of distilled water, and then stirred at 90 ° C. for 30 minutes. To this, a solution of 2.16 g (0.054 mole) of sodium hydroxide, which is 90% of the total amount of nitric acid to be produced during the reaction, is dissolved in 5 ml of distilled water, and then slowly added so that the pH of the reaction solution does not exceed 3.5. Continue to react for 30 minutes. After cooling the reaction solution, the resultant red crystalline precipitate was filtered and washed 2-3 times with distilled water, followed by drying to yield 8.64 g (yield 99.1%) of chromic picolinate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020094622A (en) * | 2001-06-12 | 2002-12-18 | 주식회사 동우 티엠씨 | A method of preparing chromium picolinate |
| CN109232404A (en) * | 2018-08-15 | 2019-01-18 | 四川新美生物科技有限公司 | A kind of preparation method of chromium picolinate |
| CN112174882A (en) * | 2020-09-29 | 2021-01-05 | 上海沃凯生物技术有限公司 | Environment-friendly preparation method of chromium picolinate |
-
1995
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020094622A (en) * | 2001-06-12 | 2002-12-18 | 주식회사 동우 티엠씨 | A method of preparing chromium picolinate |
| CN109232404A (en) * | 2018-08-15 | 2019-01-18 | 四川新美生物科技有限公司 | A kind of preparation method of chromium picolinate |
| CN112174882A (en) * | 2020-09-29 | 2021-01-05 | 上海沃凯生物技术有限公司 | Environment-friendly preparation method of chromium picolinate |
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