CN101746811A - Preparation method of basic zinc sulfate - Google Patents
Preparation method of basic zinc sulfate Download PDFInfo
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- CN101746811A CN101746811A CN200910226758A CN200910226758A CN101746811A CN 101746811 A CN101746811 A CN 101746811A CN 200910226758 A CN200910226758 A CN 200910226758A CN 200910226758 A CN200910226758 A CN 200910226758A CN 101746811 A CN101746811 A CN 101746811A
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Abstract
The invention discloses a preparation method of basic zinc sulfate, comprising the following steps: the sodium hydroxide or the ammonia water are added to the zinc sulfate solution, and the mol ratio of the ammonia and the zinc sulfate in the sodium hydroxide or the ammonia water is (1.2 - 1.8): 1, and the ammonia and the zinc sulfate have synthetic reaction under the condition that the temperature is 0Degrees Celsius - 95Degrees Celsius, pH = 5 - 9, and the reaction product is obtained after the reaction is completed; furthermore, the reaction product is washed, pressed and filtered, dried, and ground, and then the basic zinc sulfate finished product is obtained. The preparation method of basic zinc sulfate provided by the invention has advantages of low cost, wide source of raw material, full utilization of resources, environmental protection and safety, and good product quality.
Description
Technical field
The present invention relates to a kind of preparation method of compound of zinc, relate in particular to a kind of preparation method of zinc sulfate.
Background technology
In current aquaculture, the application of zinc is obligato, but all is the additive that is used as zinc element with zinc sulfate or zinc oxide generally.Zinc sulfate adopts secondary zinc oxide production more, have in addition adopt copper-cadmium slag production, removal of impurities is incomplete, cadmium content usually exceeds standard in the zinc sulfate product of production, is difficult to satisfy the requirement of fodder additives; Also there is the oxygenant residue problem in production process employing potassium permanganate etc. as oxygenant, and quality product is had negative influence.Zinc oxide is low as the biological value of additive, reach the feeding effect of high zinc, must strengthen addition, will inevitably break the balance between the various trace elements in the animal daily ration like this, cause unbalance between the nutritive ingredient, toxicity symptom appears in animal easily, and increasing addition, can influence the palatability of animal daily ration, it is unfavorable that the animal later stage is produced, and causes the environmental pollution and the wasting of resources simultaneously easily.The CN101445269A Chinese patent literature also discloses a kind of method that adopts the zinc sulfate production basic zinc sulfate of zinc oxide and outsourcing, and with the zinc source additive of this basic zinc sulfate as animal-feed, but raw material zinc oxide and zinc sulfate used in this technical scheme all mainly are outsourcings, the cost height has influenced the suitability for industrialized production and the application of basic zinc sulfate.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides that a kind of cost is low, raw material sources are extensive, the utilization of resources is abundant, the preparation method of basic zinc sulfate of Environmental Safety, good product quality.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preparation method of basic zinc sulfate, may further comprise the steps: sodium hydroxide or ammoniacal liquor are added in the zinc sulfate solution, the ammonia in described sodium hydroxide or the described ammoniacal liquor and the mol ratio of zinc sulfate are (1.2～1.8): 1, in temperature is that 0 ℃～95 ℃, pH value are to carry out building-up reactions under 5～9 the condition, obtains reaction product after reaction is finished; The basic zinc sulfate finished product will be got after reaction product washing, press filtration, drying, the pulverizing.
As further optimization and improvement to technique scheme, the present invention also provides a kind of preparation method of basic zinc sulfate, promptly do not adopt the zinc sulfate of outsourcing, and directly the zinc sulfate preparation technology of industrial chain upstream is incorporated among the basic zinc sulfate preparation technology of the present invention, it specifically may further comprise the steps: at first will carry out an acidleach in the secondary zinc oxide vitriolization solution, after an acidleach is finished reaction product is filtered, filtrate is again through once board-like press filtration, oxide treatment, after the board-like press filtration of secondary, in filtrate, add active zinc powder, again through obtaining zinc sulfate solution after three board-like press filtrations; Then sodium hydroxide or ammoniacal liquor are added in the described zinc sulfate solution, the ammonia in described sodium hydroxide or the described ammoniacal liquor and the mol ratio of zinc sulfate are (1.2～1.8): 1, in temperature is that 0 ℃～95 ℃, pH value are to carry out building-up reactions under 5～9 the condition, obtains reaction product after reaction is finished; The basic zinc sulfate finished product will be got after reaction product washing, press filtration, drying, the pulverizing.
In above-mentioned preparation method, when adopting sodium hydroxide (highly basic) as reaction raw materials, the chemical equation of this building-up reactions is as follows:
ZnSO
4·H
2O+NaOH→Zn
4(OH)
6SO
4·XH
2O+Na
2SO
4
X in the following formula is 0～7.
In above-mentioned preparation method, when adopting ammoniacal liquor (weak base) as reaction raw materials, the chemical equation of this building-up reactions is as follows:
ZnSO
4·H
2O+NH
3·H
2O→Zn
4(OH)
6SO
4·YH
2O+(NH
4)
2SO
4
Y in the following formula is 0～5.
In above-mentioned sodium hydroxide and these two kinds of reaction raw materials of ammoniacal liquor, more preferably ammoniacal liquor because the relative sodium hydroxide of ammoniacal liquor price is more cheap, has more cost advantage.
In the preparation method of basic zinc sulfate after the above-mentioned improvement, preferably the filter residue that the after-filtration gained is finished in a described acidleach carries out the secondary pickling processing, temperature when secondary pickling is handled is controlled in the scope of normal temperature to 100 ℃, the pH value is controlled at 2～3, filtrate after a filtrate behind the described secondary pickling and the described acidleach enters into described once board-like press filtration step after merging again, carries out follow-up processing.After the secondary pickling processing, raw material availability improves greatly, and cost is saved more, and the utilization of resources is more abundant, and waste discharge still less more meets the demand for development of recycling economy.
In the preparation method of basic zinc sulfate after the above-mentioned improvement, zinc and described vitriolic mol ratio contained in the described secondary zinc oxide are preferably 1: (1～1.3).According to the existing processes operational condition, the temperature during a described acidleach generally also can be controlled in the scope of normal temperature to 100 ℃, and the pH value a during acidleach generally is controlled at about 4.5.
In the preparation method of basic zinc sulfate after the above-mentioned improvement, described oxide treatment specifically can be to continue to charge into oxygen enrichment (oxygen enrichment is exactly the oxygen that carries out fully removing the high density that obtains after the denitrification with air) or air in the filtrate after described once board-like press filtration, and the temperature during described oxide treatment is preferably that 70 ℃～95 ℃, time are preferably 0.5～8h, the pH value is preferably 4.5～5.5.
In the preparation method of basic zinc sulfate after the above-mentioned improvement, the addition of described active zinc powder is generally decided according to the content of beavy metal impurities such as the copper in secondary zinc oxide and the filtrate, lead, cadmium, is generally about 1.2 times of described foreign matter content mole number.
In above-mentioned each preparation method of basic zinc sulfate, the mass concentration of described zinc sulfate solution (zinc sulfate solution when promptly carrying out building-up reactions with alkali lye) is preferably 10%～43%.
In above-mentioned each preparation method of basic zinc sulfate, the time of described building-up reactions is preferably 0.5～4h.
In above-mentioned each preparation method of basic zinc sulfate, described when dry temperature be generally 75 ℃～150 ℃.
The above-mentioned basic zinc sulfate that makes can be used as fodder additives usefulness, and zinc content can reach 47%～56.9% in the finished product, arsenic content≤5ppm, and lead content≤10ppm, cadmium content≤10ppm, the XRD figure spectrum of product is consistent with standard diagram.
Compared with prior art; the invention has the advantages that: the inventive method utilize sodium hydroxide or ammoniacal liquor under the situation of water that responds directly and zinc sulfate react; need not to add other reaction promotor; reacted product carries out can obtaining the basic zinc sulfate finished product after centrifugation, the drying; simple, convenient; the basic zinc sulfate steady quality and the detrimental impurity content that prepare are low, can satisfy the requirement of environment protection and cleaner production.With the operational path of raw material zinc oxide preparation, raw material sources of the present invention are more extensive in the prior art, and production cost also reduces greatly, by products such as the basic anacidity of product, alkali, and the vitriol of generation can further be recycled.In addition, in the technical scheme after the present invention improves, by utilizing the directly synthetic basic zinc sulfate of homemade zinc sulfate of the inventive method and sodium hydroxide or ammoniacal liquor reaction, its production cost will be significantly less than commercial zinc sulfate, and the technical scheme after improving is solution of zinc sulfate direct and sodium hydroxide or the ammoniacal liquor reaction production basic zinc sulfate that is generated by secondary zinc oxide, a plurality of links such as drying, transportation of zinc sulfate have been saved, operational path is simpler, operation easily, the price of raw materials for production is lower.
The basic zinc sulfate that makes with the present invention is as the fodder additives feeding animals, and animal not only absorbs soon, and the absorption rate height.
For example: the basic zinc sulfate fodder additives that makes with the present invention feeds pigs by the standard consumption in zinc source, can significantly improve weight gain of piglets, improves feed efficiency, improves anti-stress ability and the immunizing power of piglet, promotes piglet growth.
The basic zinc sulfate fodder additives that makes with the present invention uses the back to find that it can make the poultry speed of growth improve by the standard consumption in the zinc source poultry of feeding, and feedstuff-meat ratio descends, and can strengthen the feather glossiness of poultry, improves its stress ability, reduces mortality ratio.
The basic zinc sulfate fodder additives that makes with the present invention can strengthen its immunizing power by the standard consumption in the zinc source aquatic animal of feeding, and reduces incidence and mortality, promotes to produce, and reduces disease and takes place, and reduces water-soluble loss, improves feed coefficient.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 3;
Fig. 2 is the process flow sheet of the embodiment of the invention 4.
Embodiment
Embodiment 1:
A kind of preparation method of basic zinc sulfate of the present invention may further comprise the steps: add sulfur acid zinc (ZnSO earlier in reactor
4H
2O, the solution of zinc sulfate (mass concentration of solution of zinc sulfate is 25%) of 64.5g down together), then at normal temperatures, slowly adding sodium hydroxide 24g again, is that 50 ℃, pH value are to lower the temperature behind the isothermal reaction 1h under 6 the reaction conditions in temperature, stir cooling with water coolant, press filtration is gone into the drying room oven dry, 100 ℃ of drying temperatures, pulverize 40 mesh sieves, prepared the basic zinc sulfate finished product at last.The assay of zinc content in the finished product and arsenic, lead, cadmium is measured with reference to standard (HG 2792-1996) method of zinc oxide, and zinc content is 55.7% in this finished product, arsenic content 1.3ppm, lead content 2.5ppm, cadmium content 2.8ppm; Detect the crystal of finished product with XRD and form and structure, the XRD figure spectrum of product is consistent with standard diagram.Through the accounting of production cost, the production technique of present embodiment compared with prior art, its cost can reduce by 15% approximately.
Embodiment 2:
A kind of preparation method of basic zinc sulfate of the present invention, may further comprise the steps: the first solution of zinc sulfate (mass concentration of solution of zinc sulfate is 20%) of interpolation sulfur acid zinc 645Kg in the reactor, slowly add the ammoniacal liquor 510Kg that contains ammonia 20% again, in temperature is that 75 ℃, pH value are to lower the temperature behind the isothermal reaction 3.5h under 8 the reaction conditions, stir cooling with water coolant, 85 ℃ of oven dry of drying room are gone in press filtration, pulverize 40 mesh sieves, prepared the basic zinc sulfate finished product at last.The assay of zinc content in the finished product and arsenic, lead, cadmium is measured with reference to standard (HG 2792-1996) method of zinc oxide, and zinc content is 52.12% in this finished product, arsenic content 1.5ppm, lead content 2.0ppm, cadmium content 2.3ppm; Detect the crystal of finished product with XRD and form and structure, the XRD figure spectrum of product is consistent with standard diagram.Through the accounting of production cost, the production technique of present embodiment compared with prior art, its cost can reduce by 20% approximately; Compare as raw material with sodium hydroxide with embodiment 1, its cost can reduce about 5.7%.
Embodiment 3:
A kind of preparation method of basic zinc sulfate of the present invention as shown in Figure 1, may further comprise the steps: at first 52.28g secondary zinc oxide (zinc content is about 50%) is dissolved in the sulphuric acid soln (mass concentration is 20%) of 205ml and carries out an acidleach, temperature during an acidleach is controlled at 40 ℃, the pH value is controlled at 4.5, after an acidleach is finished reaction product is filtered, filtrate filtered is again through after the board-like press filtration once, filtrate is carried out oxide treatment, continue bubbling air in filtrate during oxide treatment, temperature during oxide treatment is controlled at 80 ℃, the pH value is controlled to be 5.0～5.2, carry out the board-like press filtration of secondary behind the oxide treatment 1.5h, and then add active zinc powder in the filtrate after the board-like press filtration of secondary, addition is the copper in the filtrate, plumbous, about 1.2 times of beavy metal impurity molar content numbers such as cadmium, remove the lead in the filtrate, heavy metals such as cadmium are 24% zinc sulfate solution through obtaining the 250ml mass concentration after three board-like press filtrations again; Slowly adding sodium hydroxide 23g then in this zinc sulfate solution, is that 90 ℃, pH value are to lower the temperature behind the isothermal reaction 3h under 8 the reaction conditions in temperature, stirs with water coolant and cools off, the blanking press filtration, go into 140 ℃ of oven dry of drying room, pulverized 60 mesh sieves, prepare the basic zinc sulfate finished product at last.The assay of zinc content in the finished product and arsenic, lead, cadmium is measured with reference to standard (HG 2792-1996) method of zinc oxide, and zinc content is 53.22% in this finished product, arsenic content 1.4ppm, lead content 2.1ppm, cadmium content 2.2ppm; Detect the crystal of finished product with XRD and form and structure, the XRD figure spectrum of product is consistent with standard diagram.
Through the accounting of production cost, the present embodiment production technique compared with prior art, its production cost can reduce by 26%.
Embodiment 4:
A kind of preparation method of basic zinc sulfate of the present invention as shown in Figure 2, may further comprise the steps: at first 52.50g secondary zinc oxide (zinc content is about 50%) is dissolved in the sulphuric acid soln (mass concentration is 27%) of 150ml and carries out an acidleach, temperature during an acidleach is controlled at 80 ℃, the pH value is controlled at 4.5, leaching time is 2h, after an acidleach is finished reaction product is filtered, the filter residue that filters gained carries out secondary pickling and handles (using sulfuric acid), temperature when secondary pickling is handled is controlled at normal temperature to 90 ℃, the pH value is controlled at 2.5, the secondary pickling time is 0.5～4h, carrying out once board-like press filtration after filtrate after a filtrate behind the secondary pickling and the acidleach merges again handles, filtrate after the board-like press filtration is once carried out oxide treatment, continue bubbling air in filtrate during oxide treatment, temperature during oxide treatment is controlled at 70 ℃, the pH value is controlled to be 5.0～5.2, carry out the board-like press filtration of secondary behind the oxide treatment 1.5h, and then add active zinc powder in the filtrate after the board-like press filtration of secondary, addition is the copper in the filtrate, plumbous, 1.15 times of beavy metal impurity molar content numbers such as cadmium, remove the lead in the filtrate, heavy metals such as cadmium are 21% zinc sulfate solution through obtaining 300ml concentration after three board-like press filtrations again; In this zinc sulfate solution, slowly add ammoniacal liquor 60g (NH then
3Mass concentration be 20%), be that 20 ℃, pH value are to lower the temperature behind the isothermal reaction 3.8h under 8.5 the reaction conditions in temperature, stir cooling with water coolant, filter press is gone into 100 ℃ of oven dry of drying room, pulverizes 60 mesh sieves, prepares the basic zinc sulfate finished product at last.The assay of zinc content in the finished product and arsenic, lead, cadmium is measured with reference to standard (HG 2792-1996) method of zinc oxide.Zinc content is 51.63% in this finished product, arsenic content 1.25ppm, lead content 2.0ppm, cadmium content 2.0ppm; Detect the crystal of finished product with XRD and form and structure, the XRD figure spectrum of product is consistent with standard diagram.Filter residue after above-mentioned secondary pickling, three the board-like press filtrations can recycle.
Through the accounting of production cost, the present embodiment production technique compared with prior art, its cost can reduce by 31%; Compare as raw material with sodium hydroxide with embodiment 3, its cost can reduce by 6.88%.
Claims (7)
1. preparation method of basic zinc sulfate, may further comprise the steps: sodium hydroxide or ammoniacal liquor are added in the zinc sulfate solution, the ammonia in described sodium hydroxide or the described ammoniacal liquor and the mol ratio of zinc sulfate are (1.2～1.8): 1, in temperature is that 0 ℃～95 ℃, pH value are to carry out building-up reactions under 5～9 the condition, obtains reaction product after reaction is finished; The basic zinc sulfate finished product will be got after reaction product washing, press filtration, drying, the pulverizing.
2. preparation method of basic zinc sulfate according to claim 1, it is characterized in that, described zinc sulfate solution is to be prepared by following steps: at first will carry out an acidleach in the secondary zinc oxide vitriolization solution, after an acidleach is finished reaction product is filtered, filtrate is again through after once board-like press filtration, oxide treatment, the board-like press filtration of secondary, in filtrate, add active zinc powder, again through obtaining zinc sulfate solution after three board-like press filtrations.
3. preparation method of basic zinc sulfate according to claim 2, it is characterized in that, the filter residue that the after-filtration gained is finished in a described acidleach carries out the secondary pickling processing, temperature when secondary pickling is handled is controlled in the scope of normal temperature to 100 ℃, the pH value is controlled at 2～3, filtrate after a filtrate behind the described secondary pickling and the described acidleach enters into described once board-like press filtration step after merging again, carries out follow-up processing.
4. according to claim 2 or 3 described preparation method of basic zinc sulfate, it is characterized in that zinc and described vitriolic mol ratio contained in the described secondary zinc oxide are 1: (1～1.3).
5. according to claim 2 or 3 described preparation method of basic zinc sulfate, it is characterized in that, described oxide treatment is to continue to charge into oxygen enrichment or air in the filtrate of pointing to after the described once board-like press filtration, and the temperature during described oxide treatment is that 70 ℃～95 ℃, time are that 0.5～8h, pH value are 4.5～5.5.
6. according to claim 1,2 or 3 described preparation method of basic zinc sulfate, it is characterized in that the mass concentration of described zinc sulfate solution is 10%～43%.
7. according to claim 1,2 or 3 described preparation method of basic zinc sulfate, it is characterized in that the time of described building-up reactions is 0.5～4h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102132774A (en) * | 2011-03-29 | 2011-07-27 | 长沙兴嘉生物工程股份有限公司 | Coating type basic salt and application thereof to animal feed additives |
| CN102502785A (en) * | 2011-10-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Preparation method of basic zinc carbonate nano powder with hexagonal and laminary structure |
| CN105399135A (en) * | 2015-11-24 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method of 5Zn(OH)2*2ZnSO4 |
| CN108863610A (en) * | 2018-09-07 | 2018-11-23 | 临沂隆信农业服务有限公司 | A kind of fertilizer for corn breeding |
| CN109264767A (en) * | 2018-11-26 | 2019-01-25 | 上海交通大学 | A kind of method of low temperature preparation nanostructure |
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2009
- 2009-12-29 CN CN2009102267586A patent/CN101746811B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102132774A (en) * | 2011-03-29 | 2011-07-27 | 长沙兴嘉生物工程股份有限公司 | Coating type basic salt and application thereof to animal feed additives |
| CN102132774B (en) * | 2011-03-29 | 2012-09-26 | 长沙兴嘉生物工程股份有限公司 | Coating type basic salt and application thereof to animal feed additives |
| CN102502785A (en) * | 2011-10-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Preparation method of basic zinc carbonate nano powder with hexagonal and laminary structure |
| CN105399135A (en) * | 2015-11-24 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method of 5Zn(OH)2*2ZnSO4 |
| CN105399135B (en) * | 2015-11-24 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of 5Zn(OH)2*2ZnSO4 |
| CN108863610A (en) * | 2018-09-07 | 2018-11-23 | 临沂隆信农业服务有限公司 | A kind of fertilizer for corn breeding |
| CN109264767A (en) * | 2018-11-26 | 2019-01-25 | 上海交通大学 | A kind of method of low temperature preparation nanostructure |
| CN109264767B (en) * | 2018-11-26 | 2022-01-14 | 上海交通大学 | Method for preparing nano structure at low temperature |
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Address after: Kang Ning Lu Hunan province 410300 Changsha Changsha Liuyang national biological industry base No. 370 Patentee after: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. Address before: 1017-1025, room 1, building 410011, Xiang Zhong central 235, Wuyi Road, Hunan, Changsha Patentee before: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. |