CN109232404A - A kind of preparation method of chromium picolinate - Google Patents
A kind of preparation method of chromium picolinate Download PDFInfo
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- CN109232404A CN109232404A CN201810928688.8A CN201810928688A CN109232404A CN 109232404 A CN109232404 A CN 109232404A CN 201810928688 A CN201810928688 A CN 201810928688A CN 109232404 A CN109232404 A CN 109232404A
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- Prior art keywords
- picoline
- temperature
- chromium
- chromium picolinate
- oxidation reaction
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- 229940046374 chromium picolinate Drugs 0.000 title claims abstract description 35
- 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 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 3
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 3
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical group O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 abstract description 9
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 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 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical group OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 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 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 108010063907 Glutathione Reductase Proteins 0.000 description 1
- 102100036442 Glutathione reductase, mitochondrial Human genes 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- MOEHVXSVUJUROX-UHFFFAOYSA-N [O-2].O.[Cr+3] Chemical compound [O-2].O.[Cr+3] MOEHVXSVUJUROX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000023852 carbohydrate metabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- OZKRURPNXOGYGD-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1 OZKRURPNXOGYGD-UHFFFAOYSA-N 0.000 description 1
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 sodium dichromate) Chemical compound 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
- C07D213/807—Processes of preparation by oxidation of pyridines or condensed pyridines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of chromium picolinate, it is the 2- picoline of 1.1~1.3:3.0:3.0~5.0: oxidant including taking mass ratio: water mixing, pH value is adjusted to 4.5~6.0, carry out oxidation reaction, the temperature of oxidation reaction is 200~240 DEG C, the pressure of oxidation reaction is 2.5~4.2MPa, and the time of oxidation reaction is 1~10h；Then lowered temperature reclamation 2- picoline again adjusts pH value to 2.0~3.0 again, carries out complex reaction under normal pressure, the temperature of complex reaction is 85~90 DEG C, and the time of complex reaction is 1~5h；Last decrease temperature crystalline, centrifugation, washing, dry obtained chromium picolinate.The present invention is using 2- picoline as starting material, 2- picoline is oxidized to by 2- pyridine carboxylic acid by aqueous oxidizing agent solution through high temperature and high pressure in acid condition, oxidant is then reduced to chromium sulfate basic, then 2- pyridine carboxylic acid and chromium sulfate basic are complexed as chromium picolinate under normal pressure, preparation methods steps are simple, product yield is high, has many advantages, such as green, environmentally friendly, at low cost.
Description
Technical field
The present invention relates to chromium picolinate technical fields, and in particular to a kind of preparation method of chromium picolinate.
Background technique
With the research and development to chromium, the mankind have realized that chromium is micro elements needed by human.At present chromium there are valences
State includes Cr2+、Cr3+And Cr6+, Cr3+It is chromium existing stable form in human body, compound participates in bone formation and albumen
The biochemical process of matter, fat, glycometabolism and insulin has facilitation to hemoglobin synthesis and hematopoiesis.But Cr6+
The metabolism that sugar, fat and the big substance of protein three are then influenced in human body, inhibits the activity of glutathione reductase, is formed with oxygen
Chromium oxide captures partial oxidation in blood, leads to body anoxic, causes dysbolism.
Chromium source is divided into inorganic chromium and Organic Chromium, and inorganic chromium (such as chromium sulfate, chromium trichloride) bioactivity is very low, biology
Utilization rate 0.4%~3% or so, the bioavailability of Organic Chromium are 10 times of inorganic chromium or more, and bioavailability is up to 10%
~25%.At present, it is considered to be the best benefit Chroma-Pak of the mankind is chromium picolinate, chromium picolinate (Chromium
Picolinate it) is also known as chromium picolinate, picolinic acid chromium is 2- pyridine carboxylic acid and Cr3+The complex compound of compound, molecular formula are
Cr(C6H4NO2)3, molecular weight 418.33 is burgundy crystals fine powder, good fluidity, is stablized under room temperature, slightly soluble
Yu Shui does not dissolve in ethyl alcohol, belongs to fat-soluble non-electrolyte, can pass through cell membrane and directly act on tissue.
Currently, there are three types of the techniques of pyridine synthesis chromic formate: 1, using 2- picoline as raw material, through potassium permanganate or weight chromium
Sour potassium and chromic anhybride etc. are oxidizing to obtain 2- pyridine carboxylic acid, adds trivalent chromium and is complexed to obtain 2- chromium picolinate.As specially
A kind of synthetic method and patent No. CN102875458B of 2- chromium picolinate disclosed in the patent of invention of benefit CN1772737A
Patent of invention disclosed in a kind of synthetic method of 2- chromium picolinate.The above method is also easy to produce a large amount of oxygen in process of production
Change the chromyl chrome green of by-product-(or chromium hydroxide) and the manganese dioxide waste residues containing manganese, and need to mistake in process
Subsequent complex reaction is carried out after filtering out again, there are cumbersome, the dangerous waste processing of giving up containing chromium is difficult.
2, using 2- vinylpyridine as raw material, 2- pyridine carboxylic acid is obtained through potassium permanganate oxidation, trivalent chromium is added and is complexed
To 2- chromium picolinate.The chromium picolinate synthesis technology disclosed such as the patent of invention of patent No. CN1408708A.The technique
In the resource scarcity of 2- vinylpyridine raw material and expensive, be unfavorable for mass production.
3, using 2- cyanopyridine as starting material, water is solvent, and sodium hydroxide is added and is hydrolyzed, and hydrolysis, which finishes, adjusts pH
Value is 3.5~5.5, and chromium chloride is added to be complexed to obtain product.The 2- pyridine as disclosed in the patent of invention of patent No. CN101602716B
One-step method disclosed in the synthetic method of chromic formate, the patent of invention of patent No. CN103319401A prepares the work of 2- chromium picolinate
A kind of synthetic method and the patent No. of chromium picolinate disclosed in skill, the patent of invention of patent No. CN103833628B
A kind of method of direct-reduction process pyridine synthesis chromic formate disclosed in the patent of invention of CN105541707A.Because of 2- cyanogen in this method
Yl pyridines fusing point is high and not soluble in water, therefore hydrolysis, in heterogeneous middle progress, the reaction time is long, while generating after hydrolyzing a large amount of
Ammonia needs absorption to handle, and the waste containing ammonia generated will cause pollution to environment, bring huge pressure to environmental protection.
Summary of the invention
That the purpose of the present invention is to provide a kind of processing steps is simple, raw material is cheap and easy to get and production process is environmentally protective,
It is suitble to the industrial production process of the chromium picolinate of industrialized production.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of chromium picolinate is the 2- methyl of 1.1~1.3:3.0:3.0~5.0 including taking mass ratio
Pyridine: oxidant: water mixing adjusts pH value to 4.5~6.0, carries out oxidation reaction, the temperature of oxidation reaction is 200~240
DEG C, the pressure of oxidation reaction is 2.5~4.2MPa, and the time of oxidation reaction is 1~10h；Then lowered temperature reclamation 2- picoline
PH value is adjusted afterwards to 2.0~3.0, carries out complex reaction under normal pressure, the temperature of complex reaction is 85~90 DEG C, complex reaction
Time is 1~5h；Last decrease temperature crystalline, centrifugation, washing, dry obtained chromium picolinate.
Further, the adjusting pH value is by the combination of one or more of addition sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid
It realizes.
Further, the oxidant is sodium dichromate, potassium bichromate, ammonium dichromate, sodium chromate, potassium chromate, chromic anhybride
One or more of combination.
Oxidant of the invention passes through the specific chemical equation of sulphur acid for adjusting pH value using sodium dichromate simultaneously:
The invention has the following advantages:
(1) using 2- picoline as starting material, pass through oxidant (such as dichromic acid through high temperature and high pressure in acid condition
Sodium) 2- picoline is oxidized to 2- pyridine carboxylic acid by aqueous solution, it is reduced to chromium sulfate basic if oxidant (such as sodium dichromate),
Then 2- pyridine carboxylic acid and chromium sulfate basic are complexed as chromium picolinate under normal pressure, the preparation method step is simple, product
High income, compared with traditional potassium permanganate oxidation complexometry and 2- cyanopyridine hydrolysis complexometry, without dangerous solid waste manganese dioxide
It is generated with ammonia-contaminated gas, is the Preparation Method of Pyridinecarboxylic Acid of the green for being really suitble to industrialized production, environmental protection, economy；
(2) cheap and from a wealth of sources using 2- picoline as starting material, production cost is low, raw material sources not
It is limited；
(3) by 2- picoline, oxidant (such as sodium dichromate), water according to mass ratio be 1.1~1.3:3.0:3.0~
5.0 mixing, proportion science, content of 6-valence Cr ions reacts remaining 2- in 1ppm hereinafter, without additional addition reducing agent after reaction
Picoline can make next raw materials for production after being distilled to recover；And oxidant (such as sodium dichromate) reduzate is alkali formula sulfuric acid
Chromium directly can carry out complex reaction with 2- pyridine carboxylic acid, without additionally using trivalent chromium；Shorten process flow and reduction is produced into
This.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
As shown in Figure 1, the preparation method of chromium picolinate provided in this embodiment includes the following steps:
(1) it takes the 2- picoline, the sodium dichromate of 246kg and the water of 400kg of 80kg to be put into reaction kettle, sulfuric acid is added
PH value is adjusted to 4.5~5.0, then heating makes 200~210 DEG C of temperature, pressure in reaction kettle be 2.5~3.2MPa, protects
Warm pressure maintaining oxidation reaction 1h；
(2) temperature in reaction kettle is down to 85~90 DEG C, vacuum distillation, distillate is 2- picoline aqueous solution, should
2- picoline aqueous solution can be used as the raw material of production next time；
(3) into the reaction kettle after being evaporated under reduced pressure plus sulfuric acid, adjust pH value to 2.0~2.5, and keep temperature be 85~
90 DEG C, complex reaction 5h, is then cooled to 20~30 DEG C and is crystallized under normal pressure, finally centrifugation, 50kg water washing, dry system
Obtain 126.2kg chromium picolinate.
Embodiment 2
The preparation method of chromium picolinate provided in this embodiment includes the following steps:
(1) it takes the 2- picoline, the potassium bichromate of 246kg and the water of 400kg of 100kg to be put into reaction kettle, salt is added
Acid for adjusting pH value is to 5.0~5.5, and then heating makes 210~230 DEG C of temperature, pressure in reaction kettle be 2.2~3.2MPa,
Heat-insulation pressure keeping oxidation reaction 10h；
(2) temperature in reaction kettle is down to 85~90 DEG C, vacuum distillation, distillate is 2- picoline aqueous solution, should
2- picoline aqueous solution can be used as the raw material of production next time；
(3) into the reaction kettle after being evaporated under reduced pressure plus hydrochloric acid, adjust pH value to 2.5~3.0, and keep temperature be 85~
90 DEG C, complex reaction 1h, is then cooled to 20~30 DEG C and is crystallized under normal pressure, finally centrifugation, 50kg water washing, dry system
Obtain 120.6kg chromium picolinate.
Embodiment 3
The preparation method of chromium picolinate provided in this embodiment includes the following steps:
(1) it takes the 2- picoline, the ammonium dichromate of 246kg and the water of 400kg of 100kg to be put into reaction kettle, phosphorus is added
Acid for adjusting pH value is to 5.0~5.5, and then heating makes 230~240 DEG C of temperature, pressure in reaction kettle be 3.2~3.5MPa,
Heat-insulation pressure keeping oxidation reaction 6h；
(2) temperature in reaction kettle is down to 85~90 DEG C, vacuum distillation, distillate is 2- picoline aqueous solution, should
2- picoline aqueous solution can be used as the raw material of production next time；
(3) into the reaction kettle after being evaporated under reduced pressure plus phosphoric acid, adjust pH value to 2.0~3.0, and keep temperature be 85~
90 DEG C, complex reaction 1h, is then cooled to 20~30 DEG C and is crystallized under normal pressure, finally centrifugation, 50kg water washing, dry system
Obtain 132.8kg chromium picolinate.
Embodiment 4
The preparation method of chromium picolinate provided in this embodiment includes the following steps:
(1) it takes the 2- picoline, the sodium chromate of 246kg and the water of 500kg of 100kg to be put into reaction kettle, nitric acid is added
PH value is adjusted to 5.0~5.5, then heating makes 230~240 DEG C of temperature, pressure in reaction kettle be 3.5~4.2MPa, protects
Warm pressure maintaining oxidation reaction 1h；
(2) temperature in reaction kettle is down to 85~90 DEG C, vacuum distillation, distillate is 2- picoline aqueous solution, should
2- picoline aqueous solution can be used as the raw material of production next time；
(3) into the reaction kettle after being evaporated under reduced pressure plus nitric acid, adjust pH value to 2.0~3.0, and keep temperature be 85~
90 DEG C, complex reaction 1h, is then cooled to 20~30 DEG C and is crystallized under normal pressure, finally centrifugation, 50kg water washing, dry system
Obtain 136.2kg chromium picolinate.
Chromium picolinate obtained by Examples 1 to 4 is subjected to Cr VI detection, does not find the presence of Cr VI.
The above is only the preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, any
The transformation and replacement that are carried out based on technical solution provided by the present invention and inventive concept should all cover the protection scope in invention
It is interior.Especially, adjusting reagent used in pH value can also be used the reagent realization of other adjustable pH value, not only this implementation
Sulfuric acid, the nitric acid, hydrochloric acid, phosphoric acid of example offer.
Claims (3)
1. a kind of preparation method of chromium picolinate, characterized by comprising: taking mass ratio is 1.1~1.3:3.0:3.0~5.0
2- picoline: oxidant: water mixing adjusts pH value to 4.5~6.0, carries out oxidation reaction, and the temperature of oxidation reaction is
200~240 DEG C, the pressure of oxidation reaction is 2.5~4.2MPa, and the time of oxidation reaction is 1~10h；Then lowered temperature reclamation 2-
PH value is adjusted after picoline to 2.0~3.0, carries out complex reaction under normal pressure, the temperature of complex reaction is 85~90 DEG C, network
The time for closing reaction is 1~5h；Last decrease temperature crystalline, centrifugation, washing, dry obtained chromium picolinate.
2. the preparation method of chromium picolinate according to claim 1, it is characterised in that: the adjusting pH value is by adding
The combination of one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid is added to realize.
3. the preparation method of chromium picolinate according to claim 1, it is characterised in that: the oxidant is dichromic acid
The combination of one or more of sodium, potassium bichromate, ammonium dichromate, sodium chromate, potassium chromate, chromic anhybride.
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Cited By (2)
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| CN116332842A (en) * | 2023-01-31 | 2023-06-27 | 四川新一美生物科技有限公司 | Preparation method for co-production of 2-chromium picolinate and chromium propionate |
| CN117658211A (en) * | 2023-12-08 | 2024-03-08 | 四川省银河化学股份有限公司 | A method for preparing high-purity hydrated chromium hydroxide and by-product sodium nicotinate |
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