CN110436512A - A kind of hydroxy chloride zinc crystal and preparation method thereof - Google Patents
A kind of hydroxy chloride zinc crystal and preparation method thereof Download PDFInfo
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- CN110436512A CN110436512A CN201910674061.9A CN201910674061A CN110436512A CN 110436512 A CN110436512 A CN 110436512A CN 201910674061 A CN201910674061 A CN 201910674061A CN 110436512 A CN110436512 A CN 110436512A
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- C01—INORGANIC CHEMISTRY
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- C01G9/00—Compounds of zinc
- C01G9/04—Halides
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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Abstract
A kind of hydroxy chloride zinc crystal of the invention and preparation method thereof belongs to II B race hydroxychloride preparation technical field.Raw material is mixed first and is ground 10 minutes using zinc hydroxide powder, zinc chloride powder as raw material by preparation method；Then mixture is sealed to reaction 3~12 hours at 40~140 DEG C；After reaction, it is cooled to room temperature, product is ground to obtain buff powder sample, as hydroxy chloride zinc crystal.The hydroxy chloride zinc crystal is the compound ZnOHCl of the composition of proportions with stoichiometric number for 1:1:1, is rhombic system crystal, space group Pna21；Pattern is the nanometer sheet of distortion, and thickness is about 30nm.The present invention utilizes solid phase-solid-phase synthesis, and process is simple, energy conservation and environmental protection, safe and efficient；The purity is high for the hydroxy chloride zinc crystal prepared, product grain is uniform, good dispersion, and property is stablized, and can be applied in numerous areas.
Description
Technical field
The invention belongs to II B race hydroxychloride preparation technical field, in particular to a kind of simple, novel, efficient system
The method of standby hydroxy chloride zinc crystal.
Background technique
Zinc has extensive trophic function, is commonly referred to as biological element, is a kind of microelement necessary to animal.Food and
Most of zinc in feed is that reference state exists, and is mainly combined with protein or amino acid, nucleic acid or phytic acid.Zinc must be from these
Releasing in compound could be absorbed by histoorgan.
Hydroxy chloride zinc, also known as basic zinc chloride, can be with Zn-ef ficiency needed for slow release animal body, relative to zinc sulfate
With the conventional zinc such as zinc oxide source, the market price is low, chemical property is stables, has that palatability is good, safe and non-toxic, dosage is few, feeding
The advantages that effect is good is supported, feed conversion rate can be improved, improves efficiency of feed utilization.The zinc that basic zinc chloride can reduce in excrement contains
Amount and soluble Zn content are conducive to protect environment, are a kind of comprehensive new zincs of ideal safe and efficient, environmentally friendly and effect
Source feed additive has broad application prospects in fields such as feed, industry, agriculturals.In addition, it is also acted as among medicine
The basic material of body and the other zinc salt products of manufacture.
Currently, the main method for preparing basic zinc chloride particle is liquid-solid synthetic method and Liquid-liquid synthetic method,
It is such as placed in saturation liquor zinci chloridi and is heated with zinc；Zinc oxide is added in liquor zinci chloridi, again added with solvent after heating；Hydrogen-oxygen
Change zinc slurry and liquor zinci chloridi Hybrid Heating；Induction system and heating etc. is added in liquor zinci chloridi and ammonium hydroxide cocurrent.Although this
A little methods can synthesize basic zinc chloride, but generally existing some disadvantages.On the one hand, these preparation methods need to control pH value,
Through filtering, centrifugation, washing, drying and other steps, operating process is complicated, and long preparation period, cost and energy consumption are higher；On the other hand,
Product obtained is impure, transformation efficiency is low, and by-product be easy to cause environmental pollution, the cost for wastewater treatment that some reactions generate
It is higher, it is difficult to realize large-scale industrial production.
The basic zinc chloride of prior art preparation is mostly the Zn of stoichiometric number 5:8:25(OH)8Cl2, with stoichiometric number
ZnOHCl for the composition of proportions of 1:1:1 has not been reported yet.
Summary of the invention
The technical problem to be solved by the present invention is to, a kind of method for proposing solid phase-synthesis in solid state ZnOHCl, and press the party
The ZnOHCl crystal that method is prepared establishes base in place of overcoming above-mentioned the deficiencies in the prior art for the further application of ZnOHCl
Plinth.
Specific technical solution is as follows:
A kind of preparation method of hydroxy chloride zinc crystal, using zinc hydroxide powder, zinc chloride powder as raw material, two raw materials
Molar ratio is 1:1；Raw material is sufficiently mixed first and is ground 10 minutes；Then mixture is sealed to reaction 3 at 40~140 DEG C
~12 hours；After reaction, it is cooled to room temperature, product is continued to grind, obtain buff powder sample, as hydroxy chloride
Zinc crystal.
During the reaction, sealing reaction, preferably 60 DEG C of reaction temperature, the reaction time preferably 6 hours.
During the reaction, described to be cooled to room temperature, product is continued to grind, preferably continues to grinding 5 minutes.
A kind of hydroxy chloride zinc crystal, which is characterized in that with stoichiometric number be the compound of the composition of proportions of 1:1:1
ZnOHCl is rhombic system crystal, and space group Pna21, crystal morphology is the nanometer sheet of distortion, with a thickness of 30nm.
The utility model has the advantages that
Compared with the prior art, the advantages of the present invention are as follows: solid phase-solid-phase synthesis is directly utilized for the first time, makes hydroxide
Zinc and zinc chloride solid directly react, and it is not necessary that any additive and catalyst is added, do not generate any byproduct of reaction and nocuousness
Substance, the reaction time is short, and the purity is high for the hydroxy chloride zinc crystal prepared, product grain is uniform, good dispersion, and property is steady
It is fixed.The present invention overcomes previous many restrictions, and process is simple, energy conservation and environmental protection, safe and efficient, is easy to realize industrial production, can also be
The numerous areas such as agricultural and chemical synthesis, chemical catalysis, photocatalysis, nano-device are applied.
Detailed description of the invention
Fig. 1 is the XRD spectra of ZnOHCl crystal prepared by embodiment 1.
Fig. 2 is the SEM figure of ZnOHCl crystal prepared by embodiment 1.
Fig. 3 is the SEM figure that the amplification factor of Cu made from embodiment 1 (OH) Cl powder becomes larger.
Fig. 4 is the XRD spectra of ZnOHCl crystal prepared by embodiment 2.
Fig. 5 is the XRD spectra of ZnOHCl crystal prepared by embodiment 3.
Fig. 6 is the XRD spectra of ZnOHCl crystal prepared by embodiment 6.
Fig. 7 is the XRD spectra of sample prepared by embodiment 7,8,9.
Specific embodiment
1 optimum condition of embodiment prepares the overall process of hydroxy chloride zinc crystal
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 6h at being 60 DEG C in temperature；After reaction, it is cooled to room temperature, product is poured into mortar and is ground
5min obtains buff powder sample.The chemical equation of the reaction is as follows: Zn (OH)2+ZnCl2=2ZnOHCl.
Fig. 1 gives the XRD spectra of prepared sample under above-mentioned condition, it was demonstrated that the sample of synthesis is hydroxy copper chloride
(ZnOHCl), sample crystallization is good, and product purity is high, and free from admixture peak occurs；Fig. 2, Fig. 3, which give, to be prepared under above-mentioned condition
The SEM of ZnOHCl crystal schemes, it can be seen that sample topography is the nanometer sheet of distortion, and thickness is about 30nm.
The present embodiment is most preferred embodiment.
2 reaction temperature of embodiment prepares the overall process of hydroxy chloride zinc crystal when slightly lower
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 6h respectively at being 50 DEG C, 40 DEG C in temperature；After reaction, it is cooled to room temperature, product is poured into and is ground
5min is ground in alms bowl, obtains buff powder sample.
Fig. 4 gives the XRD spectra of prepared sample under above-mentioned condition, it can be seen that most diffraction maximums and standard spectrum
It coincide, it was demonstrated that reacting the product of 6h respectively at being 50 DEG C, 40 DEG C in temperature is ZnOHCl, but sample crystallization is slightly poor；By sweeping
Electronic Speculum observation is retouched, light defects occurs in prepared sample topography, the nanometer sheet essentially distorted, is on a small quantity in irregular thin slice
Shape.
3 reaction time of embodiment prepares the overall process of hydroxy chloride zinc crystal when slightly shorter
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 3h respectively at being 60 DEG C, 50 DEG C, 40 DEG C in temperature；After reaction, it is cooled to room temperature, by product
It pours into and grinds 5min in mortar, obtain buff powder sample.
Fig. 5 gives the XRD spectra of prepared sample under above-mentioned condition, it can be seen that most diffraction maximums and standard spectrum
It coincide, it was demonstrated that reacting the product of 3h respectively at being 60 DEG C, 50 DEG C, 40 DEG C in temperature is ZnOHCl, but sample crystallization is slightly poor；It is logical
Electronic Speculum observation is over-scanned, light defects occurs in prepared sample topography, the nanometer sheet essentially distorted, on a small quantity in irregular
Flake.
4 reaction temperature of embodiment prepares the overall process of hydroxy chloride zinc crystal when slightly higher
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 3h, 6h, 12h respectively at being 100 DEG C in temperature；After reaction, it is cooled to room temperature, product is fallen
Enter and grind 5min in mortar, obtains buff powder sample.
By drawing XRD spectra, most of diffraction maximums can match with standard spectrum, it was demonstrated that divide at being 100 DEG C in temperature
Not Fan Ying the product of 3h, 6h, 12h be ZnOHCl, but there is new peak position to occur；It is made when temperature is slightly higher by scanning electron microscopic observation
There is pattern defect in standby sample, the nanometer sheet essentially distorted, is on a small quantity in irregular flake.
5 reaction temperature of embodiment prepares the overall process of hydroxy chloride zinc crystal when higher
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 3h, 6h, 12h respectively at being 140 DEG C in temperature；After reaction, it is cooled to room temperature, product is fallen
Enter and grind 5min in mortar, obtains buff powder sample.
By drawing XRD spectra, most of diffraction maximums can match with standard spectrum, it was demonstrated that divide at being 140 DEG C in temperature
Not Fan Ying the product of 3h, 6h, 12h be ZnOHCl, but there is new peak position to occur；It is made when temperature is slightly higher by scanning electron microscopic observation
There is bigger pattern defect in standby sample, is partially the nanometer sheet of distortion, is partially in irregular flake.
6 reaction time of embodiment prepares the overall process of hydroxy chloride zinc crystal when slightly long
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 12h at being 60 DEG C in temperature；After reaction, it is cooled to room temperature, product is poured into mortar and is ground
5min obtains buff powder sample.
Fig. 6 gives the XRD spectra of prepared sample under above-mentioned condition, it can be seen that most of diffraction maximums can be with standard
Spectrum matches, it was demonstrated that the product that 12h is reacted at being 60 DEG C in temperature is ZnOHCl, but has new peak position to occur；Pass through scanning electron microscope
Observation, it is partially the nanometer sheet of distortion that bigger pattern defect, which occurs, in prepared sample when the reaction time is slightly long, partially in not
The flake of rule.
Above embodiments 1~6, by comparison XRD spectrum it is found that temperature control is within the scope of 40~140 DEG C, time control
In 6~12h, hydroxy chloride zinc crystal can be formed.Temperature is at 60 DEG C, when the reaction time is 6h, the hydroxy chloride zinc of synthesis
Crystal structure degree is good, product purity is high.In addition, crystallinity gradually increases with the increase of temperature and time, the new peak of appearance is gradually
Increase.
Following example 7,8,9 for improperly reaction temperature and reaction time embodiment, serve as and compare, do not belong to
In protection scope of the present invention.
7 reaction time of the embodiment too long overall process that can not prepare hydroxy chloride zinc crystal
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It seals in reaction kettle, is reacted for 24 hours at being 140 DEG C in temperature；After reaction, it is cooled to room temperature, product is poured into mortar and is ground
5min is ground, white powder samples are obtained.
The XRD spectra of prepared sample is as shown in fig. 7, the main peak division for belonging to ZnOHCl of discovery originally under above-mentioned condition
For two peaks, it was demonstrated that the product reacted for 24 hours at being 140 DEG C in temperature is not ZnOHCl.
The too high overall process that can not prepare hydroxy chloride zinc crystal of 8 reaction temperature of embodiment
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, be sufficiently mixed and grind 10min；Then polytetrafluoroethyllining lining is poured the mixture into, stainless steel high pressure is put into
It is sealed in reaction kettle, reacts 3h respectively at being 180 DEG C in temperature；After reaction, it is cooled to room temperature, product is poured into mortar
5min is ground, white powder samples are obtained.
The XRD spectra of prepared sample is as shown in fig. 7, the main peak division for belonging to ZnOHCl of discovery originally under above-mentioned condition
For two peaks, it was demonstrated that reacting the product of 3h at being 180 DEG C in temperature is not ZnOHCl.
9 reaction temperature of embodiment is too low, and the time is too short, can not prepare the overall process of hydroxy chloride zinc crystal
Using zinc hydroxide powder, zinc chloride powder as raw material.0.9939g Zn (OH) is weighed first2With 1.3629g ZnCl2
It pours into mortar, is sufficiently mixed and grinds 10min, place 10min at room temperature, obtain light yellow bulk sample.
The XRD spectra of prepared sample is as shown in fig. 7, find the poor and original category of sample crystallization under above-mentioned condition
Two peaks are split into the main peak of ZnOHCl, it was demonstrated that reaction temperature is too low, and time too short product is not ZnOHCl.
Claims (4)
1. a kind of preparation method of hydroxy chloride zinc crystal, using zinc hydroxide powder, zinc chloride powder as raw material, two raw materials rub
You are than being 1:1；Raw material is sufficiently mixed first and is ground 10 minutes；Then mixture is sealed at 40~140 DEG C reaction 3~
12 hours；After reaction, it is cooled to room temperature, product is continued to grind, obtain buff powder sample, as hydroxy chloride zinc
Crystal.
2. a kind of preparation method of hydroxy chloride zinc crystal according to claim 1, which is characterized in that the sealing is anti-
It answers, reaction temperature is 60 DEG C, and the reaction time is 6 hours.
3. a kind of preparation method of hydroxy chloride zinc crystal according to claim 1 or 2, which is characterized in that described is cold
But to room temperature, product is continued to grind, is to continue with grinding 5 minutes.
4. a kind of method according to claim 1 prepares hydroxy chloride zinc crystal, which is characterized in that be to be with stoichiometric number
The compound ZnOHCl of the composition of proportions of 1:1:1 is rhombic system crystal, and space group Pna21, crystal morphology is receiving for distortion
Rice piece, with a thickness of 30 nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN113526575A (en) * | 2021-09-07 | 2021-10-22 | 吉林大学 | Nickel hydroxychloride nano material and preparation method thereof |
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| CN101941719A (en) * | 2010-05-25 | 2011-01-12 | 河北科技大学 | Method for combined production of ammonia and basic calcium chloride by decomposing ammonium chloride |
| CN107857291A (en) * | 2017-12-01 | 2018-03-30 | 广州科城环保科技有限公司 | A kind of basic zinc chloride particulate matter and preparation method thereof |
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2019
- 2019-07-24 CN CN201910674061.9A patent/CN110436512B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941719A (en) * | 2010-05-25 | 2011-01-12 | 河北科技大学 | Method for combined production of ammonia and basic calcium chloride by decomposing ammonium chloride |
| CN107857291A (en) * | 2017-12-01 | 2018-03-30 | 广州科城环保科技有限公司 | A kind of basic zinc chloride particulate matter and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN113526575A (en) * | 2021-09-07 | 2021-10-22 | 吉林大学 | Nickel hydroxychloride nano material and preparation method thereof |
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