WO2010057344A1 - 含铁结晶碱式氯化铜的制备方法及用途 - Google Patents
含铁结晶碱式氯化铜的制备方法及用途 Download PDFInfo
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- WO2010057344A1 WO2010057344A1 PCT/CN2008/073162 CN2008073162W WO2010057344A1 WO 2010057344 A1 WO2010057344 A1 WO 2010057344A1 CN 2008073162 W CN2008073162 W CN 2008073162W WO 2010057344 A1 WO2010057344 A1 WO 2010057344A1
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- Prior art keywords
- iron
- copper chloride
- solution
- copper
- chloride
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 136
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000013078 crystal Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 241001465754 Metazoa Species 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000011785 micronutrient Substances 0.000 claims abstract description 7
- 235000013369 micronutrients Nutrition 0.000 claims abstract description 7
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- VUCAVCCCXQVHAN-UHFFFAOYSA-L azane dichlorocopper Chemical compound N.Cl[Cu]Cl VUCAVCCCXQVHAN-UHFFFAOYSA-L 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003674 animal food additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- SWZCHAYJQXALJO-UHFFFAOYSA-N [Cu].C(Cl)(Cl)Cl Chemical compound [Cu].C(Cl)(Cl)Cl SWZCHAYJQXALJO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007979 citrate buffer Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000037213 diet Effects 0.000 description 2
- 235000005911 diet Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NGMTUCFCIUGWAG-UHFFFAOYSA-L [Cu+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Cu+2].[O-]Cl=O.[O-]Cl=O NGMTUCFCIUGWAG-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 210000004211 gastric acid Anatomy 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 230000003394 haemopoietic effect Effects 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940082629 iron antianemic preparations Drugs 0.000 description 1
- 230000003780 keratinization Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- 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
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- the present invention relates to a process for the preparation of a compound, and more particularly to a process for the preparation and use of an iron-containing crystalline basic copper chloride which can be used as an iron ore micronutrient element additive for animal feed.
- Copper can participate in the hematopoietic function of the body and plays an important role in the synthesis of heme and the maturation of red blood cells. Copper is involved in the osteogenesis process, pigmentation and keratinization of hair and fur in animals mainly as an essential component of various enzymes. Copper is also closely related to animal reproduction. It is a micronutrient that must be added to animal feed. It is widely used in animal husbandry at home and abroad as an animal nutritional supplement and growth promoter.
- Basic copper chloride is a copper compound that is used as an animal feed additive to overcome the drawbacks of traditional copper sulphate as a copper feed additive, such as low bioavailability, damage to nutrients in mixed feeds, and Environmental copper pollution, etc. Although basic copper chloride has the advantages of low water solubility, non-hygroscopicity, low redox ability and high bioavailability, it only supplements a trace nutrient element of animal feed.
- iron is another important trace element in animal nutrition, and iron deficiency can cause anemia in animals.
- ferrous sulfate is easy to absorb moisture and agglomerate, which is easy to antagonize with other mineral ions, resulting in a decrease in utilization rate. Increased consumption, easy to form insoluble phosphate, reduce the absorption of phosphorus and iron in animals.
- the same ferrous sulfate has redox properties, which will destroy the vitamins and oils in the feed.
- iron and copper are trace mineral nutrients that must be added to animal feed. Studies have shown that copper and iron can maintain the normal metabolism of iron in the process of animal absorption, transport and metabolism. If the copper in the diet is insufficient, the absorption of iron is blocked. In the high copper diet, iron can be added to improve copper. The growth promoting effect, therefore, iron and copper play a synergistic role in animal growth.
- Chinese Patent No. 95192983.6 discloses a 'micronutrient additive' which provides a synthetic chloroform base
- the degree of crystal grain size formed due to the instability of the reaction system is difficult to control, and the reaction time is as long as 8 hours, resulting in low production efficiency.
- Chinese Patent No. 200610060144.1 discloses a method for preparing 'oblique copper chlorite and its use'
- the reaction system is relatively stable and has high production efficiency
- the produced oblique chlorinated copper ore is a crystal having a large particle size, and the particles are distributed at 30 to 300 ⁇ m, and the particles are too large to be absorbed and utilized as a passive additive for feed additives, and oblique chlorine
- the control parameters of the copper ore type basic copper chloride production process are strictly controlled, otherwise the product is easy to agglomerate during transportation and storage, and it is difficult to uniformly mix with other mineral components.
- the present invention aims to solve the above problems, and provides a prepared iron-containing crystalline basic copper chloride which has no moisture absorption and agglomeration, good fluidity, stable chemical property, easy to mix with feed, low price, and added A method for preparing a copper-containing basic copper chloride compound which is low in cost, weakly acidic, and easily absorbable and utilized.
- the present invention provides a method for preparing iron-containing crystalline basic copper chloride, which comprises the following steps:
- ammonium chloride aqueous solution having a weight percentage of 5 to 20% by weight and a concentration of ammonium chloride of 5 to 25%, a weight percentage of 25 to 60%, a copper concentration of 50 to 200 g/L, and an iron concentration of 0.05 to 0.05. 10g/L of iron-containing copper chloride solution and 25 ⁇ 60% by weight, ammonia concentration of 2 ⁇ 20% ammonia solution or copper chloride ammonia solution with copper concentration of 0 ⁇ 200g/L, respectively, preheating To 40 to 60 degrees;
- the preheated ammonium chloride solution is first added to the reaction vessel, the iron-containing copper chloride solution and the ammonia aqueous solution or the copper chloride ammonia solution are added to the reaction vessel under stirring to control the iron-containing copper chloride solution. And the flow rate of the ammonia solution or the copper chloride ammonia solution, the pH value of the reaction material in the container is between 3 and 5, and the mixing time is 5 to 150 minutes, and the synthesis reaction is carried out at a temperature of 60 to 100 ° C to synthesize Iron-containing crystalline basic copper chloride; [14]
- the reaction equation is as follows:
- the iron-containing copper chloride solution is a printed circuit board acidic copper chloride etching waste liquid for removing heavy metal impurities such as arsenic and lead, or added by industrial grade copper chloride which removes heavy metal impurities such as arsenic. Formulated with soluble iron or ferrous salts.
- the aqueous ammonia solution is a printed circuit board ammonia chloride copper etching waste liquid for removing heavy metal impurities such as arsenic, or is prepared from industrial grade ammonia water.
- step c the volume of the material discharged from the reactor is 20 to 80% of the total volume of the reactor.
- the reaction mechanism of the present invention is to use a copper chloride solution having a relatively high iron content as a raw material, and the relatively rich iron ions participate in the crystallization process of the basic copper chloride, and promote the orthorhombic copper chloride ore.
- the crystal growth rate of the chloroform copper basic copper chloride greatly increases the production efficiency.
- the iron-containing crystalline basic copper chloride produced by the method of the present invention is mainly composed of a chloroform-type basic copper chloride, an oblique chloroform or a parat-cylite (Paratacamite).
- the basic copper chloride is a mixed phase, and the particle size distribution of 80% by weight is 10 to 50 ⁇ m.
- the iron-containing crystalline basic copper chloride prepared by the method has a copper content of 50 to 59% and an iron content of 0.03 to 5%, and is a dark green to yellow green which does not absorb moisture, does not agglomerate, and has good fluidity. powder.
- the present invention also provides the use of the iron-containing crystalline basic copper chloride prepared by the method, the iron-containing crystalline basic copper chloride prepared by the method of the invention is used as a copper-iron micronutrient element for animal feed. additive.
- the contribution of the present invention is that it effectively overcomes the defects of the existing single feed additive containing copper or iron, and overcomes the tendency of the ferrous sulfate to absorb moisture and agglomerate, which is chemically active, oxidatively destroys vitamins in the feed and Defects such as grease.
- iron is present as a water-insoluble basic salt, it is chemically stable, does not chemically react with other components in the feed such as phosphate, and does not have redox properties, and does not destroy vitamins and fats in the feed.
- the basic iron salt since the basic iron salt has water insoluble, it is soluble under weak acidity, and provides a theoretical basis for the bioavailability of the iron-containing crystalline basic copper chloride.
- Iron-containing crystalline basic copper chloride of the present invention As an animal feed trace element additive, it has good biocompatibility and does not adversely affect the environment. Therefore, it can be widely used in animal feed.
- the iron-containing crystalline basic copper chloride prepared by the method of the invention has good fluidity, does not absorb moisture, does not dust, and is easy to mix with the feed.
- the method of the invention has simple process, low production cost and is suitable for large-scale production.
- Figure 1 is an X-ray of iron-containing crystalline basic copper chloride prepared by the method of the present invention.
- FIG. 2 is a schematic diagram of a 200-fold metallographic microscope photograph of iron-containing crystalline basic copper chloride prepared by the method of the present invention.
- FIG. 2 is a circular particle having a particle diameter of 10 to 30 ⁇ m and a copper content of 57.7%, iron. The content is 0.77%.
- chlorite (Atacmite)
- chloropalite (botallackite)
- the results of the analysis are: iron-containing crystalline basic copper chloride and oblique chlorinated copper ore can be completely dissolved, the two completely dissolve between the daytime is 10 seconds and 30 seconds, and the iron-containing crystalline basic copper chloride dissolves in the inter-turn shortening Half, indicating that iron-containing crystalline copper chloride is more easily absorbed by animals than oblique copper chloride.
- the length of the dissolved turn is related to its particle size.
- the average particle size of the iron-containing crystalline copper chloride is about 20 microns, and the average diameter of the oblique copper chloride is about 100 microns.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Birds (AREA)
- Fodder In General (AREA)
Description
说明书 含铁结晶碱式氯化铜的制备方法及用途 含铁结晶碱式氯化铜的制备方法及用途
[1] 【技术领域】
[2] 本发明涉及化合物的制备方法， 特别是涉及一种可用作动物饲料的铜铁微量营 养元素添加剂的含铁结晶碱式氯化铜的制备方法及用途。
[3] 【背景技术】
[4] 铜元素可参与肌体的造血功能， 在血红素的合成和红细胞的成熟过程中起着重 要作用。 铜元素在动物体内主要是作为多种酶的必需成分而参与动物体的成骨 过程、 毛发和皮毛的色素沉着和角质化过程。 铜元素与动物的生殖也有着极为 密切的关系， 它是动物饲料必需添加的微量营养元素， 其作为动物营养补充剂 和生长促进剂， 在国内外畜牧业界已得到广泛使用。 碱式氯化铜是一种铜的化 合物， 将其用作动物饲料添加剂克服了传统的用硫酸铜作为铜饲料添加剂的缺 陷， 如生物利用率低、 对混合饲料中的营养体造成破坏及对环境的铜污染等。 碱式氯化铜虽具有水溶性低、 不吸湿、 氧化还原能力低及生物利用率高等优点 ， 但其只补充了动物饲料的一种微量营养元素铜。
[5] 另一方面， 铁在动物营养中是另一种最重要的微量元素， 缺铁会造成动物贫血
， 导致动物代谢混乱， 损害动物免疫功能， 因此铁是动物饲料中必须添加的微 量营养元素。 目前国内饲料中铁制剂仍以硫酸亚铁为主， 它具有成本低， 加工 工艺简单， 来源广泛的优点， 但硫酸亚铁易吸潮结块， 易与其他矿物离子拮抗 ， 造成利用率下降， 饲料消耗增加， 易形成不溶性磷酸盐， 降低动物对磷和铁 的吸收。 同吋硫酸亚铁具有氧化还原性， 会破坏饲料中的维生素和油脂。
[6] 如上所述， 铁和铜都是动物饲料必需添加的微量矿物营养元素。 研究表明，铜和 铁在动物吸收、 转运和代谢过程中，铜能维持铁的正常代谢， 如日粮中铜不足，则 铁的吸收受阻， 在高铜日粮中补铁，可提高铜的促生长效应， 因此， 铁和铜对动 物促生长起协同作用。
[7] 中国专利 95192983.6公开了一种'微量营养素添加剂'， 其提供的合成氯铜矿型碱
式氯化铜 （atacamite) 的方法中， 因反应体系不稳定导致生成的结晶体颗粒粗细 程度难于控制， 且反应吋间长达 8小吋， 导致生产效率过低。 200610060144.1 号中国专利公开了一种'斜氯铜矿的制备方法及其用途'， 其
反应体系虽然比较稳定， 生产效率高， 但是生成的斜氯铜矿是粒径较大的结晶 体， 颗粒分布在 30到 300微米， 而颗粒太大不利于作为饲料添加剂被动物体吸收 利用， 且斜氯铜矿型碱式氯化铜生产过程反应参数的控制要求严格， 否则产品 在运输和贮存过程中容易结块， 难以均匀地和其他矿物成分混合。
[8] 【发明内容】
[9] 本发明旨在解决上述问题， 而提供一种所制备的含铁结晶碱式氯化铜具有不吸 潮结块， 流动性好， 化学性质稳定、 易于和饲料配合， 价格低廉、 添加成本低 ， 弱酸性可溶， 易于吸收利用的含铁结晶碱式氯化铜化合物的制备方法。
[10] 本发明的目的还在于提供由本发明的方法所制备的含铁晶碱式氯化铜的用途。
[11] 为实现上述目的， 本发明提供一种含铁结晶碱式氯化铜的制备方法， 该方法包 括如下步骤：
[12] a
、 分别取重量百分比为 5〜20%、 氯化铵重量百分比浓度为 5〜25%的氯化铵水 溶液， 重量百分比为 25〜60%、 铜浓度为 50〜200g/L、 铁浓度为 0.05〜10g/L的 含铁氯化铜溶液及重量百分比为 25〜60%、 氨重量百分比浓度为 2〜20%的氨水 溶液或铜浓度为 0〜200g/L的氯化铜氨液， 分别预热至 40〜60度；
[13] b
、 将预热的氯化铵溶液先加入到反应容器中、 含铁氯化铜溶液及氨水溶液或氯 化铜氨液在搅拌条件下同吋加入到反应容器中， 控制含铁氯化铜溶液及氨水溶 液或氯化铜氨液的流量， 使容器内反应物料的 pH值在 3〜5之间， 加料吋间为 5〜 150分钟， 在温度为 60〜100°C进行合成反应， 以合成含铁结晶碱式氯化铜； [14] 该反应方程式如下：
[15] 2CuC12 + 3NH3 + 3H20 = Cu2(OH)3Cl | + 3NH4C1
[16] Cu2(OH)3Cl + FeCB + 3NH3 + 3H20 = Cu2(OH)3Cl-Fe(OH)3 | + 3NH4C1 [17] c
、 当含铁结晶碱式氯化铜颗粒生长至平均粒径为 10〜50微米吋停止进料， 并从 底部放出一部分物料， 排出物料中的沉淀经洗涤、 抽滤、 离心， 得到含铁结晶 碱式氯化铜。 物料中的母液以后可代替氯化铵溶液用作步骤 a的缓冲溶液。
[18] 步骤 a中， 所述含铁氯化铜溶液为除去砷、 铅等重金属杂质的印制线路板酸性 氯化铜蚀刻废液， 或由除去砷等重金属杂质的工业级氯化铜加入可溶性铁盐或 者亚铁盐配制而成。
[19] 步骤 a中， 所述氨水溶液为除去砷等重金属杂质的印制电路板氨性氯化铜蚀刻 废液， 或由工业级氨水配制。
[20] 步骤 c中， 从反应器中放出的物料的体积为反应器总体积的 20〜80%。
[21] 本发明的反应机理在于使用含铁比较高的氯化铜溶液为原料， 其比较丰富的铁 离子参与了碱式氯化铜结晶过程， 促进了正交晶系氯铜矿
型碱式氯化铜晶核的形成和结晶生长。 同吋抑制了单斜晶系斜氯铜矿型碱式氯 化铜 （botallackite) 结晶的生长， 因此有利于稳定氯铜矿型碱式氯化铜 的合成反应体系。 由于本合成反应体系比较稳定， 可提高温度以加快
氯铜矿型碱式氯化铜的结晶生长速度， 使得生产效率大幅度提高。 本发明的方 法生成的含铁结晶碱式氯化铜是以氯铜矿型碱式氯化铜为主， 斜氯铜矿型和副 氯铜矿 (Paratacamite)
碱式氯化铜为辅的混合相， 占其重量的 80%的粒径分布在 10〜50微米。 且该方法 制备的含铁结晶碱式氯化铜的铜含量为 50〜59%， 铁含量为 0.03〜5%， 是一种不 吸潮、 不结块、 流动性良好的深绿色至黄绿色粉末。
[22] 本发明还提供了由该方法所制备的含铁结晶碱式氯化铜的用途， 由本发明的方 法所制备的含铁结晶碱式氯化铜用作动物饲料的铜铁微量营养元素添加剂。
[23] 本发明的贡献在于， 它有效克服了现有的单一含铜或铁的饲料添加剂的缺陷， 并克服了硫酸亚铁易吸潮结块， 化学性质活泼， 氧化破坏饲料中的维生素和油 脂等缺陷。 由于铁是以不溶于水的碱式盐存在， 化学性质稳定， 不会与饲料中 其他成分例如磷酸盐起化学反应， 也不具有氧化还原性质， 不破坏饲料中的维 生素和油脂。 还由于碱式铁盐具有水不溶， 但弱酸性下可溶的特性， 为含铁结 晶碱式氯化铜的生物可利用性提供了理论依据。 本发明的含铁结晶碱式氯化铜
作为动物饲料微量元素添加剂， 其生物适口性好， 不会对环境造成不利影响， 因此， 可以在动物饲料中普遍添加使用。 由本发明的方法制得的含铁结晶碱式 氯化铜的流动性好， 不吸潮， 不扬尘， 易于和饲料配合均匀。 本发明的方法工 艺简单， 生产成本低， 适合规模化生产。
[24] 【附图说明】
[25] 图 1是本发明的方法制备的含铁结晶碱式氯化铜的 X射线
衍射谱图鉴定对比示意图。
[26] 图 2是本发明的方法制备的含铁结晶碱式氯化铜的 200倍金相显微镜照片示意图
[27] 【具体实施方式】
[28] 下列实施例是对本发明的进一步解释和说明， 对本发明不构成任何限制。
[29] 一、 含铁结晶碱式氯化铜的制备：
[30] 取工业级固体氯化铵 400公斤加入到 8M3玻璃钢反应罐中， 注入自来水 1500升， 边通入蒸汽边搅拌使氯化铵溶解并预热至 75°C， 补充少量水至 2M3。 另将铜离子 含量 100克 /升、 铁离子含量 1300毫克 /升、 pH值为 2的精制酸性氯化铜蚀刻废液以 及 6%的氨水各 3.0M3 , 分别在各自的原料储罐中预热至 75°C。 启动反应罐搅拌桨 ， 同吋幵启铜废液和氨水的原料泵并调整流量计流速， 使二者分别以约 50升 /分 钟的速度加入到反应罐中， 保持反应温度 80°C、 pH值为 4， 反应 60分钟后关闭原 料泵停止加料。 在搅拌状态下打幵反应罐底部阀门， 将 2/3即 5.0M3的物料排到真 空抽滤器中抽滤， 再用自来水分次冲洗、 抽滤， 得到含铁结晶碱式氯化铜约 400 公斤。
[31] 二、 含铁结晶碱式氯化铜的形貌和含量分析：
[32] 本发明的方法所制备的含铁结晶碱式氯化铜的 200倍显微镜照片如图 2所示， 它 是粒径 10〜30微米的圆形颗粒， 其铜含量为 57.7% , 铁含量为 0.77%。
[33] 三、 含铁结晶碱式氯化铜晶型结构分析：
[34] 用 X射线衍射仪检测可知， 本发明的方法所制备的含铁结晶碱式氯化铜
为氯铜矿 (Atacmite) 、 斜氯铜矿 (botallackite)
和三方氯化铜 （Paratacamite) 结构的混合物， 其 X射线衍射谱图鉴定对比
见图 1。
[35] 四、 弱酸性溶液中的溶解速度对比试验：
[36] 测定含铁结晶碱式氯化铜在模拟动物胃酸环境下的弱酸性溶液中的溶解度和溶 解速度， 同吋测定按 200610060144.1号专利的方法制备的斜氯铜矿型碱式氯化铜 的溶解度和溶解速度如下：
[37] 用 10克柠檬酸、 10克柠檬酸铵、 2毫升浓盐酸溶解于 1升蒸馏水， 配制成 p H 值为 3.7的弱酸性溶液柠檬酸铵缓冲溶液。
[38] 分析步骤为： 准确称取 O.lg碱式氯化铜， 并置于带盖三角瓶中， 分别加入 100毫 升弱酸性溶液柠檬酸铵缓冲溶液， 在 37±1°C恒温水浴振荡， 测定其溶解吋间。
[39] 分析结果为： 含铁结晶碱式氯化铜和斜氯铜矿都能全部溶解， 两者完全溶解吋 间为 10秒和 30秒， 含铁结晶碱式氯化铜溶解吋间缩短一半， 表明含铁结晶碱式 氯化铜比斜氯铜矿更容易被动物吸收利用。 溶解吋间的长短与其粒径相关， 含 铁结晶碱式氯化铜平均粒径约 20微米， 而斜氯铜矿平均粒径约 100微米。
Claims
[1] 一种
含铁结晶碱式氯化铜的制备方法， 其特征在于， 该方法包括如下步骤： a
、 分别取重量百分比为 5〜20%、 氯化铵重量百分比浓度为 5〜25%的氯化 铵水溶液， 重量百分比为 25〜60%、 铜浓度为 50〜200g/L、 铁浓度为 0.05 〜10g/L的含铁氯化铜溶液及重量百分比为 25〜60%、 氨重量百分比浓度为 2〜20%的氨水溶液或铜浓度为 0〜200g/L的氯化铜氨液， 分别预热至 40〜6 0度；
b
、 将预热的氯化铵溶液先加入到反应容器中、 含铁氯化铜溶液及氨水溶液 或氯化铜氨液在搅拌条件下同吋加入到反应容器中， 控制含铁氯化铜溶液 及氨水溶液或氯化铜氨液的流量， 使容器内反应物料的 pH值在 3〜5之间， 加料吋间为 5〜150分钟， 在温度为 60〜100°C进行合成反应， 以合成含铁结 晶碱式氯化铜；
C
、 当含铁结晶碱式氯化铜颗粒生长至平均粒径为 10〜50微米吋停止进料， 并从底部放出一部分物料， 排出物料中的沉淀经洗涤、 抽滤、 离心， 得到 含铁结晶碱式氯化铜。
[2] 如权利要求 1所述的方法， 其特征在于， 步骤 a中， 所述含铁氯化铜溶液为 除去砷、 铅等重金属杂质的印制线路板酸性氯化铜蚀刻废液， 或由除去砷 等重金属杂质的工业级氯化铜加入可溶性铁盐或者亚铁盐配制而成。
[3] 如权利要求 1所述的方法， 其特征在于， 步骤 a中， 所述氨水溶液为除去砷 等重金属杂质的印制电路板氨性氯化铜蚀刻废液， 或由工业级氨水配制。
[4] 如权利要求 1所述的方法， 其特征在于， 步骤 c中， 从反应器中放出的物料 的体积为反应器总体积的 20〜80%。
[5] 如权利要求 1的方法所制备的含铁结晶碱式氯化铜用作动物饲料的铜铁微量 营养元素添加剂。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602979A (zh) * | 2012-04-01 | 2012-07-25 | 廖勇志 | 碱式氯化铜的制备方法 |
| CN111642633A (zh) * | 2020-07-07 | 2020-09-11 | 武汉轻工大学 | 碱式氯化铜微球及其制备方法、以及饲料添加剂 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659555A (en) * | 1984-05-12 | 1987-04-21 | Th. Goldschmidt Ag 03 | Process for the preparation of basic copper carbonate |
| CN1528171A (zh) * | 2003-10-16 | 2004-09-15 | 黄逸强 | 碱式氯化铜饲料添加剂及其制备方法 |
| CN101434405A (zh) * | 2008-11-10 | 2009-05-20 | 深圳市危险废物处理站有限公司 | 含铁结晶碱式氯化铜的制备方法及用途 |
-
2008
- 2008-11-24 WO PCT/CN2008/073162 patent/WO2010057344A1/zh active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659555A (en) * | 1984-05-12 | 1987-04-21 | Th. Goldschmidt Ag 03 | Process for the preparation of basic copper carbonate |
| CN1528171A (zh) * | 2003-10-16 | 2004-09-15 | 黄逸强 | 碱式氯化铜饲料添加剂及其制备方法 |
| CN101434405A (zh) * | 2008-11-10 | 2009-05-20 | 深圳市危险废物处理站有限公司 | 含铁结晶碱式氯化铜的制备方法及用途 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602979A (zh) * | 2012-04-01 | 2012-07-25 | 廖勇志 | 碱式氯化铜的制备方法 |
| CN102602979B (zh) * | 2012-04-01 | 2014-05-28 | 廖勇志 | 碱式氯化铜的制备方法 |
| CN111642633A (zh) * | 2020-07-07 | 2020-09-11 | 武汉轻工大学 | 碱式氯化铜微球及其制备方法、以及饲料添加剂 |
| CN111642633B (zh) * | 2020-07-07 | 2023-01-06 | 武汉轻工大学 | 碱式氯化铜微球及其制备方法、以及饲料添加剂 |
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