CN104944462B - Preparation method for feed grade zinc oxide - Google Patents
Preparation method for feed grade zinc oxide Download PDFInfo
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- CN104944462B CN104944462B CN201510403827.1A CN201510403827A CN104944462B CN 104944462 B CN104944462 B CN 104944462B CN 201510403827 A CN201510403827 A CN 201510403827A CN 104944462 B CN104944462 B CN 104944462B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 176
- 238000000034 method Methods 0.000 claims abstract description 157
- 230000008569 process Effects 0.000 claims abstract description 138
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000002386 leaching Methods 0.000 claims abstract description 85
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 74
- 239000011701 zinc Substances 0.000 claims abstract description 68
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 60
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 34
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 28
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 28
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 67
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 53
- 239000000047 product Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 32
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000003002 pH adjusting agent Substances 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002594 sorbent Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011667 zinc carbonate Substances 0.000 claims description 7
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 7
- 241001249696 Senna alexandrina Species 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 230000007306 turnover Effects 0.000 claims description 6
- 230000002977 hyperthermial effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical group [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017906 NH3H2O Inorganic materials 0.000 abstract 2
- 235000016804 zinc Nutrition 0.000 description 60
- 239000012535 impurity Substances 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- BMXIKZGQMSADGS-UHFFFAOYSA-N azane;carbonic acid;sulfuric acid Chemical compound N.OC(O)=O.OS(O)(=O)=O BMXIKZGQMSADGS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 235000019155 vitamin A Nutrition 0.000 description 2
- 239000011719 vitamin A Substances 0.000 description 2
- 229940045997 vitamin a Drugs 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- -1 ClO-Salt Substances 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 208000034189 Sclerosis Diseases 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
- 229930003268 Vitamin C Natural products 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method for feed grade zinc oxide. Secondary zinc oxide-zinc calcine containing 78% of ZnO serves as a raw material, and a (NH4)2SO4 solution and a NH3H2O solution serve as a lixivium; the preparation method comprises the steps of zinc calcine leaching treatment, arsenic removing treatment, heavy metal removing treatment, ammonia distillation-zinc sinking treatment, calcining treatment and the like, and the (NH4)2SO4 solution and the NH3H2O solution in the preparing process can be recycled repeatedly. According to the preparation method for the feed grade zinc oxide, the obtained zinc oxide has the advantages of being low in cost, high in purity, strong in activity and strong in product applicability, and a wide industrial application prospect is obtained.
Description
Technical field
The present invention relates to feed grade zinc oxide technical field, specifically refers to a kind of preparation method of feed grade zinc oxide.
Background technology
Found according to animal nutrition research：Zinc is the important composition composition of various enzymes and hormone, and zinc is to hereditary information
Transmission and the biosynthesis of protein have indirectly to be affected.Zinc is relevant with the function of vitamin, and zinc supplementation can reduce vitamin A
Metabolism, and have synergy with vitamin A, artery sclerosis can be prevented, maintain twenty-twenty vision.Zinc is also cooperateed with vitamin C
Effect, and animal skeleton is normally formed important.
Zinc source in feed includes inorganic zinc and organic zinc；Inorganic zinc mainly has zinc oxide, zinc sulfate, zinc chloride etc.；Oxygen
It is the best a kind of feed zinc source of biological nutrition function in all inorganic zincs to change zinc.With feed grade monohydrate zinc sulphate and seven water sulphur
The additives containing zinc feed such as sour zinc are compared, feed grade zinc oxide
With being difficult, deliquescence, matter are fine and smooth, micro- Zn content is high, product is fine, be easier to the features such as absorbing, its biology
Utilization rate is high.And no matter zinc sulfate is better than at aspects such as feed manufacturing, ferrous stability, hygroscopicity, the stability of vitamin,
It is good zinc source.Zinc oxide compared with other zinc sources, beneficial to feed addictive cost is reduced, add by unit zinc low cost
Amount is equivalent to the 44% of monohydrate zinc sulphate, the 28% of white vitriol, and economic benefit is also more preferable.
Feed grade zinc oxide replaces the inexorable trend that zinc sulfate is feed zinc source.Such as replace common oxygen with activated zinc oxide
Change zinc and come used as fodder zinc source, activated zinc oxide is compared with common zinc oxide：With proportion it is less, absorb be more easy to, make raising move
Thing digestion function of stomach and intestine is more preferable, the advantage that biology utilization rate is higher and cost is lower.
The content of the invention
It is an object of the invention to provide a kind of preparation method of feed grade zinc oxide, with low cost, purity height, particle diameter
Little, the active strong, advantage of product strong applicability.
The present invention can be achieved through the following technical solutions：
The invention discloses a kind of preparation method of feed grade zinc oxide, comprises the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4Solution, NH3•H2O solution is leachate, and in secondary oxidative zinc-zinc calcine (NH is separately added into4)2SO4Solution, NH3•H2O
Solution obtains leaching mixed solution, controls zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O is 1:（1.1～1.3）∶
（2.2～2.6）, it is subsequently adding pure water and adjusts secondary oxidative zinc-zinc calcine solid masses with the volume for leaching mixed solution
Solid-to-liquid ratio is 1g：6～7ml carries out Leach reaction, keeps Leach reaction temperature to be 60～70 DEG C and persistently leaches 1～3h, is treated
The preliminary leaching system for processing；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+It is molten
Liquid as precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:（1.8～2.2）Relation add oxidant, controlling reaction temperature between 60～70 DEG C, constant temperature stirring
1～3h, adds pH adjusting agent to adjust leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine after cooling
Raw material：FeSO4For 50:（0.8～1.2）Relation add FeSO4Precipitated sorbent, is stirred for 0.5～1.5h, filters after turnover
Take the leaching system that filtrate obtains arsenic removal process；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, first process in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in leaching system：BaS is 50:（0.8～1.2）Relation add
BaS, according to quality proportioning secondary oxidative zinc-zinc calcine raw material after filtration：Zinc powder is 50:（0.8～1.2）Relation add
Zinc powder, then controlling reaction temperature 60～70 DEG C keep reaction 3～5h, obtain removing heavy metals process after leaching system；
D, ammonia still process-heavy zinc are processed：First carry out ammonia still process process, c step obtained by removing heavy metals process after leaching system according to
Quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:（2.7～3.3）Relation add NH4HCO3, at intensification
Managing and connecting with suction ammoniacal liquor in the external distillation cascade of leaching system carries out absorption ammonia, adjusts the feed liquid that system is leached during ammonia still process
Concentration controls azeotropic for 108 DEG C and continues in 1.1～1.3mol/L, leaches system after boiling starts certain hour and starts
Existing white casse phenomenon ammonia is absorbed from after distillation pipework condensation by suction ammoniacal liquor, and ammonia still process is terminated after ammonia still process 10min again after muddiness；Steam
Ammonia is cooled down after terminating, and the leaching system after the completion of ammonia still process is according to quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3
For 50:（0.8～1.2）Relation add NH4HCO3, stir 0.3～0.7 hour, it is passed through CO under normal pressure26～8h of gas, entirely
Journey stirs to reaction and terminates to complete heavy zinc process, at the beginning of filtering to obtain process feed liquid and presoma solid head product, presoma solid
Product drying is obtained presoma ZnCO3Solid；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, controls calcining heat for 280
DEG C～350 DEG C persistently calcine 1～3h, you can obtain prepare zinc oxide product.
In a steps, secondary oxidative zinc-zinc calcine is selected as raw material, with wide material sources, advantage with low cost, but
It is contain in zinc calcine plurality of impurities while to there is also, the problem high to product purity processing requirement, the product for finally preparing in addition
Product zinc oxide is used as feed addictive, it is necessary to this is considered during subsequent technique.In order to ensure to leach
Rate, promotes Chemical Kinetics to move towards product direction, and integrated cost considers, controls zinc oxide：(NH4)2SO4、NH3•H2O
Mole ratio be 1:（1.1～1.3）∶（2.2～2.6）, leaching rate had both been effectively ensured, avoid causing increasing emptily for cost again；
It is 1g that secondary oxidative zinc-zinc calcine solid masses is adjusted with the solid-to-liquid ratio of the volume for leaching mixed solution：6～7ml, both avoided
The too low reaction rate caused to kinetics of concentration is excessively slow, and the leaching that excessive concentration is caused in thermodynamics of reactions is prevented effectively from again
Go out the too low impact of rate；It it is 60～70 DEG C by controlling reaction temperature, it is to avoid temperature is too low to be caused instead to Chemical Kinetics
The impact for answering speed excessively slow, while it also avoid the too high problem for causing energy consumption cost too high of temperature；Leached by control and continued
Time is 1～3h, it is to avoid extraction time is too short to cause the too low impact for not making full use of raw material of leaching rate, turn avoid leaching
Going out overlong time causes the cost that the excessive waste of energy consumption is produced to increase severely.At the same time, above parameters are interactively with each other in a steps
Affect, respectively chemically impact of the angle of kinetics angle and chemical reaction thermodynamics to leaching rate, chemical reaction is moved
The speed that mechanics influence reaction is carried out, directly reflects the cost of Leaching Systems, and what the leaching of chemical reaction thermodynamic effects was realized can
Energy property, determines the purity and quality of product, and above response parameter is pulled one hair and move the whole body, even if the simple change of single parameter
Reaction effect can be produced directly affects, and each response parameter must integrally consider that all kinds of of different parameters can directly contribute
The greatest differences of reaction effect.
In b steps, (NH is selected4)2S2O8It is that each condition such as integrated cost, removal of impurities is produced to zinc oxide as oxidant
Affect what is formed, compared with other oxidants, ClO-Salt, KMnO4Introduce new impurity, H2O2、Fe2+、O3Presence blasts air oxygen
The effect of removing arsenic for changing trivalent arsenic is bad, and Product checking can not reach HG2792-1996 standards, and NH4)2S2O8Become after reduction
（NH4）2SO4, product do not affect the running of whole production procedure.New impurity is not introduced, and becomes one of mother liquor in system
Point；Select Fe2+Solution, as precipitating reagent, is also the running for considering the system such as production procedure and follow-up removal of impurities, because molysite can
It is converted into colloid and there can be preferable precipitation adsorption performance；CaO is selected as pH adjusting agent, CaO meetings during input
Heat is produced, the purpose that pH is adjusted both had been realized, the carrying out that system range temperature promotes chemical reaction, and most end form can be improved again
Into Ca2+It is also to common are machine adding ingredient in feed, without the need for extra removing；Control secondary oxidative zinc-zinc calcine is former
Material：(NH4)2S2O8Quality proportioning 50:（1.8～2.2）With secondary oxidative zinc-zinc calcine raw material：FeSO4Treatment proportioning be
50:（0.8～1.2）, the addition for both having avoided oxidant and precipitated sorbent very few causes arsenic removal thoroughly not make to product purity
Into impact, the addition that oxidant and precipitated sorbent are prevented again excessively introduces the pair that new impurity is caused to the place of production of product
Effect；It it is 60～70 DEG C by controlling reaction temperature, it is to avoid temperature is too low to cause reaction rate excessively slow Chemical Kinetics
Impact, while it also avoid the too high problem for causing energy consumption cost too high of temperature；1～3h, addition are stirred by controlling constant temperature
Precipitated sorbent stirs 0.5～1.5h, it is to avoid the reaction time is too short to cause, except the adequacy for affecting arsenic removal reaction to carry out, to keep away again
Exempt from the cost that the reaction time long excessive waste for causing energy consumption produces to increase severely.At the same time, b step in above parameters that
This reciprocal effect, respectively chemically impact of the angle of kinetics angle and chemical reaction thermodynamics to effect of removing arsenic, changes
The speed that kinetics affects reaction to carry out is learned, directly reflects the cost of arsenic removal system, chemical reaction thermodynamic effects arsenic removal
The quality of effect, determines the purity and quality of product, and above response parameter is pulled one hair and move the whole body, even if the letter of single parameter
Altered can be produced on reaction effect directly to be affected, and each response parameter must integrally consider that all kinds of meetings of different parameters are straight
Connect the greatest differences for causing reaction effect.
In c step removing heavy metals are processed, select BaS and zinc powder as reagent, be based in technological process as far as possible not
The consideration of new impurity is mixed into, using BaS and zinc powder removing heavy metals.S in BaS2- can be complete by contamination precipitation, Ba2+
Can be by the SO4 in system2-Removing is precipitated, and does not introduce new impurity, it is relatively low using BaS costs.Add zinc powder
The also bigger foreign metal of commercial weight, its oxidation product is Zn2+, foreign metal can form simple substance and be filtered to remove；By control time
Level zinc oxide-zinc calcine raw material：The quality proportioning of BaS is 50:（0.8～1.2）, secondary oxidative zinc-zinc calcine raw material：Zinc
The quality proportioning of powder is 50:（0.8～1.2）, both avoid the addition for removing Heavy Metal Reagent from very few causing heavy metals removal not
The impact for thoroughly causing to product purity, the addition that heavy metals removal additive is prevented again excessively introduces new impurity to product
The side effect that causes of the place of production；It it is 60～70 DEG C by controlling reaction temperature, it is to avoid temperature is too low to be made to Chemical Kinetics
Into the impact that reaction rate is excessively slow, while it also avoid the too high problem for causing energy consumption cost too high of temperature；By keeping reaction 3
～5h, it is to avoid the reaction time is too short to cause, except the adequacy for affecting to go removing heavy metals reaction to carry out, to turn avoid the reaction time
The cost that the long excessive waste for causing energy consumption is produced increases severely.At the same time, above parameters impact interactively with each other in c steps,
The chemically impact of the angle heavy metal removal effect of kinetics angle and chemical reaction thermodynamics respectively, chemical reaction
The cost of removing heavy metals system, a chemical reaction thermodynamic effects huge sum of money are removed in the speed that kinetic effect reaction is carried out, directly reflection
The quality of category removal effect, determines the purity and quality of product, and above response parameter is pulled one hair and move the whole body, even if single ginseng
Several simple changes can be produced on reaction effect directly to be affected, and each response parameter must integrally consider, different parameters it is each
Class can directly contribute the greatest differences of reaction effect.
In d steps, with the growth of time of ammonia distillation, the increase of solid zinc amount, to be added in heavy zinc operation afterwards
NH4HCO3Amount also gradually to increase, but the CO to be passed through2Gas in growth, the feed liquid of time of ammonia distillation but with being complexed zinc
The reduction of amount and reduce, but, the time of spinning out just not only will consume energy source more, also produce considerable influence to sinking zinc process below, because
This, ammonia still process is terminated after ammonia still process 10min after muddiness again.Secondary zinc oxide-zinc calcine raw material before by controlling ammonia still process：NH4HCO3's
Quality proportioning is 50:（2.7～3.3, secondary oxidative zinc-zinc calcine raw material during heavy zinc：NH4HCO3Quality proportioning be
50:（0.8～1.2）, the addition for both having avoided reagent very few causes presoma ZnCO3Solids of sedimentation is not exclusively received to product
The impact of rate, prevents impact that the excessively multipair product purity of addition of reagent causes again and to waste the production cost that reagent causes empty
Increase；The feed concentration of system is leached during by adjusting ammonia still process in 1.1～1.3mol/L, stirring 0.3～0.7 hour, normal pressure
Under be passed through CO26～8h of gas, effectively chemically the angle of kinetics ensures the abundant raising yield of precipitation, it is to avoid concentration
The excessive process for being unfavorable for subsequent calcination of the too high presoma particle diameter to gained, avoids that concentration is too low, the reaction time is long, front again
Drive body particle diameter is too small to cause the reaction time long, production cost high；Selection adds at twice NH4HCO3Solution, effectively
Ensure that the adequacy that reaction is carried out, it is ensured that the presoma particle diameter of gained is more uniform, and Impurity removal is more thorough, and product purity is more
It is high.
In e step calcination processings, with calcination time growth or the rising of temperature, zinc oxide product purity gradually increases,
But the high of cost is also caused thereupon, therefore, control calcining heat for 280 DEG C～350 DEG C and persistently calcine 1～
3h.Meanwhile, the aggregate particle size of ZnO begins with a trend of increase from 250 DEG C, gradually stable to after 350 DEG C, controls calcining heat
The uniformity for ensureing gained zinc oxide particle diameter is not only improved for 280 DEG C～350 DEG C, the specific surface area that zinc oxide is effectively ensured again exists
One, than larger scope, is improved the biologically active of zinc oxide, is more suitably applied to as feed addictive.
Step a, b, c, d, e in the technical scheme of the preparation method of feed grade zinc oxide of the present invention, included is respectively walked
Based on step before, the adjustment of either step individual parameters, all subsequent step can be caused different degrees of impact and
The change of correspondence parameter, and finally it is embodied in the aspects such as purity, yield, cost, the biologically active of product.
Preferably, described (NH4)2SO4Solution, NH3•H2To recycle solution, the d is walked at ammonia still process-heavy zinc O solution
Suction ammoniacal liquor in reason walks gained process feed liquid during ammonia still process-heavy zinc is processed, the last preparation gained for last preparation process d
During process feed liquid remains to be processed as the step zinc calcine leaching process of preparation process a next time as remaining feed liquid outside this absorbing liquid
Leachate.(NH4)2SO4After circular response, original state is returned to again.Carried out after heavy zinc step in technological process
Filter, be mainly (NH4)2SO4The process feed liquid of solution, by containing (NH4)2SO4Process feed liquid carry out reclaim profit
With, again next time leach in be used.NH3·H2O is returned to original state again after series reaction.In technique
When carrying out ammonia still process step process in flow process, while the ammonia for steaming is absorbed.And it is with last remaining process material
Liquid is absorbed.Again mainly containing (NH4)2SO4And NH3·H2The process feed liquid of O is recycled, and is soaked next time again
It is used in taking.In actual production, process feed liquid after repeatedly circulation, (NH4)2SO4The rate of recovery it is substantially left 90%
It is right.NH3·H2The rate of recovery of O is substantially 45% or so.And the rate of recovery of product purity and zinc is all that comparison is high.Pass through
(NH4)2SO4Solution, NH3•H2The recycling of O solution, discharges without accessory substance generation, also without air-polluting gas；Together
When, the utilization that moves in circles of process feed liquid.Substantially Zero-discharge non-pollution is realized, is clean and environment-friendly production.It is also social friendly
Type industry, it will with good economic results in society.
Preferably, a is walked in the zinc calcine leaching process process, zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O
For 1: 1.2: 2.4, the secondary oxidative zinc-zinc calcine solid masses is 1g with the solid-to-liquid ratio of the volume for leaching mixed solution：
6ml or 7ml, the Leach reaction temperature is 60 DEG C or 70 DEG C.
Preferably, during the b steps arsenic removal is processed, the secondary oxidative zinc-zinc calcine raw material：(NH4)2S2O8Quality match somebody with somebody
Than for 50:2, the reaction temperature at 60 DEG C or 70 DEG C, the secondary oxidative zinc-zinc calcine raw material：FeSO4Quality proportioning
For 50:1.
Preferably, during the c steps removing heavy metals are processed, secondary oxidative zinc-zinc calcine raw material：The quality proportioning of BaS is
50:1, the secondary oxidative zinc-zinc calcine raw material：The quality proportioning of zinc powder is 50:1, the reaction temperature is 60 DEG C or 70
℃。
Preferably, during the d steps ammonia still process-heavy zinc is processed, the secondary oxidative zinc-zinc calcine raw material added before ammonia still process：
NH4HCO3Quality proportioning be 50:Secondary oxidative zinc-zinc calcine raw material during heavy zinc described in 3：NH4HCO3Quality proportioning
For 50:1.
A kind of preparation method of feed grade zinc oxide of the present invention, with following beneficial effect：
The ZnO that the present invention is prepared has purity height (content is up to 99.9%), high activity (specific surface area average out to
50m2/ more than g), particle diameter little (10～20nm), spherical, containing mesopore (average 15nm or so) the characteristics of.And impurities
Amount meets multinomial zinc oxide national sector standard up to (As≤0.00035%, Pb≤0.00014%, Cd≤0.00018% etc.).With
ZnO prepared by other methods is compared has the advantages that low cost, purity are high, particle diameter is little, active strong, product strong applicability.And
And, the present invention ammonium sulfate, ammoniacal liquor, also have in the middle of produce carbon dioxide can be with recycle and reuse.Other materials form filter
Slag, filter residue can be reclaimed and do construction material use.Some precious metals can pursue the proper method and be recycled, in the present invention
In technological process, discharge without accessory substance generation, also without air-polluting gas, feed liquid is also the utilization that moves in circles.Substantially
Zero-discharge non-pollution is realized, is clean and environment-friendly production.It is also social friendly industry, it will imitate with good social economy
Benefit.
Specific embodiment
In order that those skilled in the art more fully understand technical scheme, with reference to embodiment to this
Bright product is described in further detail.
Embodiment 1
The invention discloses a kind of preparation method of feed grade zinc oxide, comprises the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4Solution, NH3•H2O solution is leachate, and in secondary oxidative zinc-zinc calcine (NH is separately added into4)2SO4Solution, NH3•H2O
Solution obtains leaching mixed solution, controls zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O is 1: 1.3: 2.6, then
It is 1g to add pure water to adjust secondary oxidative zinc-zinc calcine solid masses with the solid-to-liquid ratio of the volume for leaching mixed solution：6ml
Leach reaction is carried out, keeps Leach reaction temperature persistently to leach 2h for 65 DEG C, obtain pending preliminary leaching system；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+It is molten
Liquid as precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:2 relation adds oxidant, and between 65 DEG C, constant temperature stirring 2h is added controlling reaction temperature after cooling
PH adjusting agent adjusts leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine raw material：FeSO4For 50:2
Relation add FeSO4Precipitated sorbent, is stirred for 1.5h, and the leaching system that filtrate obtains arsenic removal process is filtered to take after turnover；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, first process in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in leaching system：BaS is 50:0.8 relation adds BaS, mistake
According to quality proportioning secondary oxidative zinc-zinc calcine raw material after filter：Zinc powder is 50:0.8 relation adds zinc powder, then controls
Reaction temperature keeps reaction 5h at 60 DEG C, obtains the leaching system after removing heavy metals are processed；
D, ammonia still process-heavy zinc are processed：First carry out ammonia still process process, c step obtained by removing heavy metals process after leaching system according to
Quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:2.7 relation adds NH4HCO3, hyperthermic treatment and
The external distillation cascade of leaching system is connected with suction ammoniacal liquor and carries out absorption ammonia, and the feed concentration for adjusting leaching system during ammonia still process exists
1.2mol/L, controls azeotropic for 108 DEG C and continues, and it is existing that the system that leaches after boiling starts certain hour starts to occur white casse
As ammonia is absorbed from after distillation pipework condensation by suction ammoniacal liquor, ammonia still process is terminated after ammonia still process 10min again after muddiness；Ammonia still process is cooled down after terminating,
Leaching system after the completion of ammonia still process is according to quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:1 relation
Add NH4HCO3, stir 0.5 hour, it is passed through CO under normal pressure2Gas 7h, whole process stirs to reaction and terminates to complete heavy zinc process,
Process feed liquid and presoma solid head product are filtered to obtain, the drying of presoma solid head product is obtained presoma ZnCO3Gu
Body；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, controls calcining heat for 300
DEG C persistently calcine 2h, you can obtain the zinc oxide product for preparing.
Embodiment 2
The invention discloses a kind of preparation method of feed grade zinc oxide, comprises the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4Solution, NH3•H2O solution is leachate, and in secondary oxidative zinc-zinc calcine (NH is separately added into4)2SO4Solution, NH3•H2O
Solution obtains leaching mixed solution, controls zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O is 1: 1.1: 2.2, then
It is 1g to add pure water to adjust secondary oxidative zinc-zinc calcine solid masses with the solid-to-liquid ratio of the volume for leaching mixed solution：6ml
Leach reaction is carried out, keeps Leach reaction temperature persistently to leach 2h for 65 DEG C, obtain pending preliminary leaching system；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+It is molten
Liquid as precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:2 relation adds oxidant, and between 60 DEG C, constant temperature stirring 1h is added controlling reaction temperature after cooling
PH adjusting agent adjusts leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine raw material：FeSO4For 50:
0.8 relation adds FeSO4Precipitated sorbent, is stirred for 1h, and the leaching system that filtrate obtains arsenic removal process is filtered to take after turnover；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, first process in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in leaching system：BaS is 50:1 relation adds BaS, filters
Afterwards according to quality proportioning secondary oxidative zinc-zinc calcine raw material：Zinc powder is 50:1.2 relation adds zinc powder, then controls anti-
Answer temperature that reaction 5h is kept at 60 DEG C, obtain the leaching system after removing heavy metals are processed；
D, ammonia still process-heavy zinc are processed：First carry out ammonia still process process, c step obtained by removing heavy metals process after leaching system according to
Quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:3.1 relation adds NH4HCO3, hyperthermic treatment and
The external distillation cascade of leaching system is connected with suction ammoniacal liquor and carries out absorption ammonia, and the absorbing liquid is d steps ammonia still process-heavy zinc in embodiment 1
Process feed liquid obtained by process, process feed liquid is remained next time as the remaining feed liquid outside the absorbing liquid of embodiment 2 in embodiment 1
Preparation is used, and is adjusted and leach during ammonia still process the feed concentration of system in 1.2mol/L, is controlled azeotropic for 108 DEG C and is continued,
Boiling starts to leach system after certain hour and starts to occur white casse phenomenon ammonia and absorbed by suction ammoniacal liquor from after distillation pipework condensation, treats
Terminate ammonia still process after ammonia still process 10min again after muddiness；Ammonia still process is cooled down after terminating, and the leaching system after the completion of ammonia still process is matched somebody with somebody according to quality
Than secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:1 relation adds NH4HCO3, stir 0.5 hour, lead under normal pressure
Enter CO2Gas 6h, whole process stirs to reaction and terminates to complete heavy zinc process, filters to obtain process feed liquid and presoma solid primiparity
Product, presoma solid head product drying is obtained presoma ZnCO3Solid；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, controls calcining heat for 280
DEG C persistently calcine 3h, you can obtain the zinc oxide product for preparing.
Embodiment 3
The invention discloses a kind of preparation method of feed grade zinc oxide, comprises the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4Solution, NH3•H2O solution is leachate, and the leachate is the process material obtained by d steps ammonia still process in embodiment 1-heavy zinc process
In example 2 d walks remaining feed liquid unnecessary outside absorbing liquid for liquid application, is separately added in secondary oxidative zinc-zinc calcine
(NH4)2SO4Solution, NH3•H2O solution obtains leaching mixed solution, controls zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O
It is worth for 1: 1.2: 2.4, is subsequently adding pure water and adjusts secondary oxidative zinc-zinc calcine solid masses and leach the body of mixed solution
Long-pending solid-to-liquid ratio is 1g：7ml carries out Leach reaction, keeps Leach reaction temperature persistently to leach 1h for 70 DEG C, obtains pending
Preliminary leaching system；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+It is molten
Liquid as precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:2.2 relation adds oxidant, and at 60 DEG C, constant temperature stirring 3h is added controlling reaction temperature after cooling
PH adjusting agent adjusts leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine raw material：FeSO4For 50:1
Relation add FeSO4Precipitated sorbent, is stirred for 1h, and the leaching system that filtrate obtains arsenic removal process is filtered to take after turnover；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, first process in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in leaching system：BaS is 50:1.2 relation adds BaS, mistake
According to quality proportioning secondary oxidative zinc-zinc calcine raw material after filter：Zinc powder is 50:1.1 relation adds zinc powder, then controls
Reaction temperature keeps reaction 3h at 70 DEG C, obtains the leaching system after removing heavy metals are processed；
D, ammonia still process-heavy zinc are processed：First carry out ammonia still process process, c step obtained by removing heavy metals process after leaching system according to
Quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:3 relation adds NH4HCO3, hyperthermic treatment is simultaneously in leaching
Take the external distillation cascade of system and connect and carry out absorption ammonia with ammoniacal liquor is inhaled, the absorbing liquid is at d steps ammonia still process in embodiment 2-sink zinc
Process feed liquid obtained by reason, adjusts and leach during ammonia still process the feed concentration of system in 1.3mol/L, controls azeotropic for 108 DEG C
And continue, the system that leaches after boiling starts certain hour starts white casse phenomenon ammonia occur from after distillation pipework condensation by suction ammonia
Liquid absorbs, and ammonia still process is terminated after ammonia still process 10min again after muddiness；Ammonia still process is cooled down after terminating, and the leaching system after the completion of ammonia still process is pressed
According to quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:1.2 relation adds NH4HCO3, stir 0.3 little
When, it is passed through CO under normal pressure2Gas 8h, whole process stirs to reaction and terminates to complete heavy zinc process, filters to obtain process feed liquid and forerunner
Body solid head product, presoma solid head product drying is obtained presoma ZnCO3Solid；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, controls calcining heat for 350
DEG C persistently calcine 1h, you can obtain the zinc oxide product for preparing.
Embodiment 4
The invention discloses a kind of preparation method of feed grade zinc oxide, comprises the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4Solution, NH3•H2O solution is leachate, and the leachate is the process material obtained by d steps ammonia still process in embodiment 2-heavy zinc process
In embodiment 3 d walks remaining feed liquid unnecessary outside absorbing liquid for liquid application, is separately added in secondary oxidative zinc-zinc calcine
(NH4)2SO4Solution, NH3•H2O solution obtains leaching mixed solution, controls zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O
It is worth for 1: 1.2: 2.4, is subsequently adding pure water and adjusts secondary oxidative zinc-zinc calcine solid masses and leach the body of mixed solution
Long-pending solid-to-liquid ratio is 1g：6.5ml carries out Leach reaction, keeps Leach reaction temperature persistently to leach 1.5h for 670 DEG C, obtains waiting to locate
The preliminary leaching system of reason；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+It is molten
Liquid as precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:2 relation adds oxidant, and at 60 DEG C, constant temperature stirring 3h adds pH to adjust to controlling reaction temperature after cooling
Section agent adjusts leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine raw material：FeSO4For 50:1 pass
System adds FeSO4Precipitated sorbent, is stirred for 1h, and the leaching system that filtrate obtains arsenic removal process is filtered to take after turnover；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, first process in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in leaching system：BaS is 50:1 relation adds BaS, filters
Afterwards according to quality proportioning secondary oxidative zinc-zinc calcine raw material：Zinc powder is 50:1.2 relation adds zinc powder, then controls anti-
Answer temperature that reaction 3h is kept at 70 DEG C, obtain the leaching system after removing heavy metals are processed；
D, ammonia still process-heavy zinc are processed：First carry out ammonia still process process, c step obtained by removing heavy metals process after leaching system according to
Quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:3.3 relation adds NH4HCO3, hyperthermic treatment and
The external distillation cascade of leaching system is connected with suction ammoniacal liquor and carries out absorption ammonia, and the absorbing liquid is d steps ammonia still process-heavy zinc in embodiment 3
Process feed liquid obtained by process, adjusts and leach during ammonia still process the feed concentration of system in 1.2mol/L, controls azeotropic for 108
DEG C and continue, the system that leaches after boiling starts certain hour starts to occur white casse phenomenon ammonia and is inhaled from after distillation pipework condensation
Ammoniacal liquor absorbs, and ammonia still process is terminated after ammonia still process 10min again after muddiness；Ammonia still process is cooled down after terminating, the leaching system after the completion of ammonia still process
According to quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:1.2 relation adds NH4HCO3, stir 0.5 little
When, it is passed through CO under normal pressure2Gas 8h, whole process stirs to reaction and terminates to complete heavy zinc process, filters to obtain process feed liquid and forerunner
Body solid head product, presoma solid head product drying is obtained presoma ZnCO3Solid；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, controls calcining heat for 350
DEG C persistently calcine 2h, you can obtain the zinc oxide product for preparing.
At the same time, for the technique effect of valid certificates technical solution of the present invention, to using the embodiment of the present invention 1～4
Zinc oxide obtained by preparation carries out the test of correlated performance and characterizes, and concrete outcome is as shown in table 1；
Table 1, zinc oxide performance test and characterization result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Method of testing | |
| Zinc oxide content（%） | 99.93 | 99.91 | 99.92 | 99.94 | EDTA compleximetries |
| Lead content（%） | 0.00012 | 0.00011 | 0.00013 | 0.00010 | GB13080 |
| Cadmium content（%） | 0.00013 | 0.00017 | 0.00015 | 0.00013 | GB13082 |
| Arsenic content（%） | 0.00028 | 0.00025 | 0.00031 | 0.00029 | GB/T 610.1 |
| Specific surface area（m2/g） | 65.32 | 70.28 | 62.83 | 87.91 | BET adsorbs a desorption method |
| Average pore size（nm） | 14.85 | 17.65 | 15,37 | 15,01 | BET adsorbs a desorption method |
| Average grain diameter（nm） | 17.28 | 16.33 | 15.89 | 19.62 | Laser particle size method |
As can be seen from Table 1, the ZnO that the present invention is prepared has purity height (content is up to 99.9%), high activity (ratio
Surface area average out to 50m2/ more than g), particle diameter little (10～20nm), spherical, containing mesopore (average 15nm or so) the characteristics of.
And impurities amount meets multinomial zinc oxide state up to (As≤0.00035%, Pb≤0.00014%, Cd≤0.00018% etc.)
Family's professional standard.Compared with ZnO prepared by other methods with low cost, purity is high, particle diameter is little, active strong, product is suitable for
The strong advantage of property.
Additionally, in order to be analyzed using the commercial viability of circulation technology to technical solution of the present invention, in conjunction with the embodiments 1
～4 Matter Transfer service conditions, process costs and existing such as sulfuric acid-ammonium hydrogen carbonate technique technical solution of the present invention,
Ammonia-ammonium hydrogen carbonate technique is contrasted with zinc calcine (containing ZnO78%) as raw material, and concrete outcome is as shown in table 2：
The comparison that table 2, three kind of process costs are consumed
As can be seen from Table 2, economic core, as raw material, is carried out to produce 1t ZnO consumable materials with zinc calcine (containing ZnO78%)
Calculation can obtain table 2.It is found that the cost of 13686 yuan/t of present invention process is than relatively low, if removing three kinds of materials participates in circulation
The utilization that moves in circles of ammoniacal liquor and ammonium sulfate in cost, i.e. present invention process, material cost will drop to 1200 yuan/t or so.Than passing
Two kinds of techniques of sulfuric acid-ammonium bicarbonate method and ammonia-ammonium bicarbonate method of system have cost advantage, and this law has preferably economic effect
Benefit.
Therefore, technical solution of the present invention adopts secondary oxidative zinc for raw material, heavy by ammonia-ammonia sulfate leaching-carbon dioxide
Zinc method produces activated zinc oxide, with raw material sources extensively, process is simple, small investment, zinc recovery are high, energy consumption is little, produce into
The advantages of this is low, environment friendly and pollution-free, have broad application prospects,
The above, only presently preferred embodiments of the present invention not makees any pro forma restriction to the present invention；It is all
The those of ordinary skill of the industry can shown in by specification and the above and swimmingly implement the present invention；But, it is all to be familiar with
Professional and technical personnel makes in the range of without departing from technical solution of the present invention using disclosed above technology contents
A little change, modification with develop equivalent variations, be the present invention Equivalent embodiments；Meanwhile, all realities according to the present invention
Change, modification and differentiation of any equivalent variations that matter technology is made to above example etc., still fall within the technology of the present invention
Within the protection domain of scheme.
Claims (2)
1. a kind of preparation method of feed grade zinc oxide, it is characterised in that comprise the following steps：
A, zinc calcine leaching process process：With ZnO content be 78% secondary oxidative zinc-zinc calcine as raw material, with (NH4)2SO4It is molten
Liquid, NH3•H2O solution is leachate, and in secondary oxidative zinc-zinc calcine (NH is separately added into4)2SO4Solution, NH3•H2O solution
Obtain leaching mixed solution, control zinc oxide：(NH4)2SO4、NH3•H2The mole ratio of O is 1: 1.2: 2.4, is subsequently adding
It is 1g that pure water adjusts secondary oxidative zinc-zinc calcine solid masses with the solid-to-liquid ratio of the volume for leaching mixed solution：6 or 7mL enter
Row Leach reaction, keeps Leach reaction temperature to be 60 or 70 DEG C and persistently leaches 1～3h, obtains pending preliminary leaching system；
B, arsenic removal are processed：With (NH4)2S2O8As oxidant, CaO as pH adjusting agent, in the basic conditions with Fe2+Solution is made
For precipitating reagent, in preliminary leaching system pending obtained by a steps according to quality proportioning secondary oxidative zinc-zinc calcine raw material：
(NH4)2S2O8For 50:2 relation adds oxidant, and controlling reaction temperature is between 60 or 70 DEG C, and constant temperature stirs 1～3h, cold
But pH adjusting agent is added to adjust leaching system for alkaline then according to quality proportioning secondary oxidative zinc-zinc calcine raw material afterwards：
FeSO4For 50:1 relation adds FeSO4Precipitated sorbent, is stirred for 0.5～1.5h, filtrate is filtered to take after turnover and obtains arsenic removal
The leaching system of process；
C, removing heavy metals process：With BaS, zinc powder as removing heavy metals reagent treatment, the leaching for first processing in the arsenic removal obtained by b steps
First according to quality proportioning secondary oxidative zinc-zinc calcine raw material in system：BaS is 50:1 relation adds BaS, presses after filtration
According to quality proportioning secondary oxidative zinc-zinc calcine raw material：Zinc powder is 50:1 relation adds zinc powder, then controlling reaction temperature
3～5h of reaction is kept at 60 or 70 DEG C, the leaching system after removing heavy metals are processed is obtained；
D, ammonia still process-heavy zinc are processed：Ammonia still process process is first carried out, the leaching system after removing heavy metals obtained by c steps are processed is according to quality
Proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:3 relation adds NH4HCO3, hyperthermic treatment is simultaneously in leaching body
Be external distillation cascade carries out absorption ammonia with inhaling ammoniacal liquor and connect, adjust the feed concentration of leaching system during ammonia still process 1.1～
1.3mol/L, controls azeotropic for 108 DEG C and continues, and it is existing that the system that leaches after boiling starts certain hour starts to occur white casse
As ammonia is absorbed from after distillation pipework condensation by suction ammoniacal liquor, ammonia still process is terminated after ammonia still process 10min again after muddiness；Ammonia still process is cooled down after terminating,
Leaching system after the completion of ammonia still process is according to quality proportioning secondary oxidative zinc-zinc calcine raw material：NH4HCO3For 50:1 relation
Add NH4HCO3, stir 0.3～0.7 hour, it is passed through CO under normal pressure26～8h of gas, whole process stirs to reaction and terminates to complete
Heavy zinc process, filters to obtain process feed liquid and presoma solid head product, and the drying of presoma solid head product is obtained presoma
ZnCO3Solid；
E, calcination processing：To the presoma ZnCO obtained by d steps3Solid carries out calcination processing, control calcining heat for 280 DEG C～
350 DEG C are persistently calcined 1～3h, you can obtain the zinc oxide product for preparing.
2. the preparation method of feed grade zinc oxide according to claim 1, it is characterised in that：(the NH4)2SO4Solution,
NH3•H2To recycle solution, the suction ammoniacal liquor during the d steps ammonia still process-heavy zinc is processed steams O solution for last preparation process d step
Gained process feed liquid in ammonia-heavy zinc process, the last gained process feed liquid for preparing is used as remaining outside this absorbing liquid
Feed liquid remains to walk the leachate during zinc calcine leaching process is processed as preparation process a next time.
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| CN108689427B (en) * | 2018-06-08 | 2020-11-10 | 广州科城环保科技有限公司 | Method for recovering feed-grade zinc oxide from basic zinc chloride production mother liquor and application thereof |
| CN110482592B (en) * | 2019-08-19 | 2022-02-11 | 西北矿冶研究院 | Process for preparing nano zinc oxide from steelmaking ash |
| CN111874877A (en) * | 2020-08-13 | 2020-11-03 | 昆明冶金研究院有限公司 | Method for efficiently removing arsenic from Na2SeSO3 solution |
| CN112408460B (en) * | 2020-12-10 | 2022-09-13 | 平江县吉成科技有限责任公司 | Preparation method of nano zinc oxide |
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| CN1028768C (en) * | 1992-04-28 | 1995-06-07 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
| US20050112041A1 (en) * | 2003-11-21 | 2005-05-26 | Horne Deane A. | Method for producing higher purity zinc oxide |
| CN102583503B (en) * | 2011-01-18 | 2013-07-17 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
| CN102627313B (en) * | 2012-04-12 | 2013-09-11 | 广汉隆达饲料有限公司 | Wet production process for feed-grade active zinc oxide |
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