CN105819489B - A kind of green synthesis method of stannous chloride - Google Patents
A kind of green synthesis method of stannous chloride Download PDFInfo
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- CN105819489B CN105819489B CN201610138917.7A CN201610138917A CN105819489B CN 105819489 B CN105819489 B CN 105819489B CN 201610138917 A CN201610138917 A CN 201610138917A CN 105819489 B CN105819489 B CN 105819489B
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- stannous chloride
- hydroxylamine hydrochloride
- synthesis method
- soluble
- green synthesis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a kind of green synthesis method of stannous chloride, reduces soluble cupric salt using hydroxylamine hydrochloride and prepares stannous chloride, concretely comprises the following steps：Soluble cupric salt is soluble in water, hydroxylamine hydrochloride is added at certain temperature and certain stir speed (S.S.), continues stirring reaction for a period of time after adding, centrifugation, washing, alcohol are washed and are dried in vacuo to obtain the stannous chloride of white.Present invention process route is simple, easy to operate, and reaction condition is gentle, and the reaction time is short, efficiency high, is adapted to large-scale production.
Description
Technical field
The invention belongs to the synthesis technical field of stannous chloride, and in particular to a kind of green synthesis method of stannous chloride.
Background technology
Stannous chloride is a kind of butter, is tetrahedral crystal shape or white cubic crystal, and appearance color is white
Or pale powder, sometimes with loose spot shape.Stannous chloride is slightly soluble in water, poisonous, easy photodissociation, deliquescence, is placed in air easily
It is oxidized to the basic copper chloride of green（Cu2(OH)3Cl）, in the hot water rapid hydrolysis generation stannous chloride hydrate and in white
Color.The more prominent position of occupation ratio in chlorine derivative product, stannous chloride are commonly used in organic synthesis industry and rubber industry
Catalyst, such as vinyl acetate, one chlorobutadiene of production, acrylonitrile, second diene ethyl-acetylene etc. are prepared by raw material of ethene,
Diphenyl ether polymerization catalyst can be prepared with diamines；Stannous chloride can be used as desulfurizing agent, release agent and take off in petro chemical industry
Toner；It is used as catalyst, reducing agent and flocculating agent in oil and fat chemical, it is especially more famous with catalyst；In the production of dyestuff
Except producing aniline dyes, phthalocyanine blue, phthalocyanine green, the emerald green pigment of activity are risen outside mantoquita mating reaction, are also serving as condensing agent, catalysis
Agent and reducing agent；In silicone industry, the stannous chloride of high activity is urged as what methyl chloride silane mixture monomer synthesized
Agent is the most important purposes of stannous chloride.High activity stannous chloride is crystalline powder of the particle without coherent condition, and its structure is dredged
Pine, but specific surface area is big, has small-size effect, surface and an interfacial effect, quantum size effect etc., such stannous chloride it is outer
See and physical arrangement is all more complicated, because its activity is high, therefore by the nanoscale stannous chloride that certain technique synthesizes in catalysis work
It is widely used in skill.Additionally there is extensive use in metallurgical industry, electroplating industry, medical industry and agriculture chemicals fungicide industry
On the way.
The method of traditional mode of production stannous chloride mainly has：Copper wire air oxidation process, the method reaction speed is slow, material and energy
Consumption height and copper wire price height and limited source；Copper sulfate method, production cost is high and reaction produces a large amount of acid mist pollution environment, system
Product granularity it is tiny be not easy to filter, product easily aoxidizes；Copper scrap chlorine direct oxidation method, the method are direct using industrial chlorine
Oxidation, therefore equipment anticorrosion and production environmental safety are poor；Copper scrap hydrochloric acid method, only limits copper scrap mud on the method raw material, Ying Fu in mud
Containing cupric oxide, otherwise need to add cupric oxide, reaction rate is low, long action time, and product purity is not high.
In addition, the eutectic that Luo Genxiang etc. is mixed to form using chlorination copper powders and copper powder as raw material in urea and Choline Chloride
Stannous chloride is prepared in solvent（CN101928034 A）, dissolving of the method to some reactants be limited and liquid temperature scope
It is small, limit application of the pure eutectic solvent as reaction dissolvent.Ying Tao is opened etc. prepares stannous chloride using ionic liquid
（CN100513315C）, this method is to add the raw material into ionic liquid to be reacted, so as to reduce the pollution to environment,
And can be recycled after ionic liquid is separated, but produced because ionic liquid is prepared in cost, biodegradability and preparation process
The problems such as raw discarded object, its green still suffers from dispute.Wang Baoluo etc. prepares stannous chloride using hydrothermal reduction method
（CN1235806C）, this method is that copper sulphate and sodium chloride are made into mixed solution regulation acidity to be transferred to pressure-resistant corrosion-resistant reaction
Kettle, adds excessive red copper powder, and heating is flowed back, and hydrochloric acid is added after reacting completely and is made stannous chloride, but this method due to
Hydro-thermal method feature itself is HTHP so as to make it have very big danger.Therefore a kind of effective, energy simple to operate is developed
Consume relatively low and environment-friendly method and carry out synthesizing chlorinated cuprous be very important.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of stannous chloride simple to operate, easily controllable and green
Green synthesis method.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of green synthesis method of stannous chloride,
It is characterized in that concretely comprise the following steps：Soluble cupric salt and sodium acetate is soluble in water, add under conditions of 15-25 DEG C of stirring
Enter the reducing agent hydroxylamine hydrochloride aqueous solution or hydroxylamine hydrochloride solid is reacted, centrifuge, wash after reacting completely, alcohol is washed and vacuum is done
It is dry to obtain target product stannous chloride, wherein soluble cupric salt is CuCl2·2H2O、CuBr2、Cu(NO3)2·3H2O or
CuSO4·5H2O, the mol ratio of soluble cupric salt and hydroxylamine hydrochloride is 1:0.1-4.
Further limit, the mol ratio of described sodium acetate and soluble cupric salt is 1-3:1.
The green synthesis method of stannous chloride of the present invention, it is characterised in that concretely comprise the following steps：By soluble divalence
Mantoquita is soluble in water, adds the reducing agent hydroxylamine hydrochloride aqueous solution in 5-30 DEG C or hydroxylamine hydrochloride solid is reacted, reaction is complete
Centrifugation, washing, alcohol are washed and are dried in vacuo to obtain target product stannous chloride afterwards, wherein soluble cupric salt is Cu (OAc)2·
H2O, the mol ratio of soluble cupric salt and hydroxylamine hydrochloride is 1:0.5-5.
Further limit, the dosage of described aqueous solvent is that the volume that 1mmol solubility cupric salts correspond to water is 0.5-
30mL。
Further limit, stir speed (S.S.) is controlled during adding the reducing agent hydroxylamine hydrochloride aqueous solution or hydroxylamine hydrochloride solid
For 250-2000r/min, the time control of the reducing agent hydroxylamine hydrochloride aqueous solution is added in 1-10min.
Further to limit, the reaction time that the addition reducing agent hydroxylamine hydrochloride aqueous solution or hydroxylamine hydrochloride solid are reacted is
5-30min。
Further limit, described vacuum drying temperature is 25-70 DEG C, vacuum drying time 10-20h.
The present invention has the advantages that compared with prior art：
1st, reaction system is simple, only with soluble cupric salt during target product is prepared（Copper source）, water（It is molten
Agent）And hydroxylamine hydrochloride（Reducing agent）, and they belong to general chemistry reagent, it is cheap and easy to get；
2nd, reaction environment is gentle（Normal temperature and pressure）, process is simply easily controllable, no bazardous waste discharge, raw for green
Production, has very big environmental benefit；
3rd, present invention process is simple, and the reaction time is short, efficiency high, is adapted to large-scale production, has very big economic benefit.
Brief description of the drawings
Fig. 1 is the XRD of stannous chloride made from the embodiment of the present invention 1, meets JCPDS standard cards 6-0344 chlorination
The standard diagram of cuprous crystal.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
By 0.01mol Cu (OAc)2·H2O is dissolved in 20mL water, under 5 DEG C and 250-500r/min of stir speed (S.S.)
The 0.005mol hydroxylamine hydrochloride aqueous solution is added dropwise（2mL）, time for adding control is in 1-5min；After adding, continue to stir 10min, from
The heart, washing, alcohol are washed, and are placed in vacuum drying chamber and are obtained the stannous chloride of white in 30 DEG C of dry 20h.Product is surveyed through XRD
Examination, meet the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 2
By 0.01mol Cu (OAc)2·H2O is dissolved in 20mL water, in 25 DEG C and 1000-1500r/min stir speed (S.S.)
The lower dropwise addition 0.005mol hydroxylamine hydrochloride aqueous solution（5mL）, time for adding control is in 5-10min；After adding, continue to stir 30min,
Centrifugation, washing, alcohol are washed, and are placed in vacuum drying chamber and are obtained the stannous chloride of white in 50 DEG C of dry 15h.Product is through XRD
Test, meet the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 3
By 0.01mol Cu (OAc)2·H2O is dissolved in 50mL water, in 30 DEG C and 1000-1500r/min stir speed (S.S.)
The lower dropwise addition 0.005mol hydroxylamine hydrochloride aqueous solution（10mL）, time for adding control is in 5-10min；After adding, continue to stir
40min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the stannous chloride of white in 50 DEG C of dry 15h.Product
Tested through XRD, meet the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 4
By 0.01mol Cu (OAc)2·H2O is dissolved in 100mL water, in 25 DEG C and 1500-2000r/min of stirring speed
0.01mol solid hydroxylamine hydrochlorides are slowly added under rate, continue to stir 50min, centrifugation, washing, alcohol are washed, and are placed on vacuum drying
In case the stannous chloride of white is obtained in 50 DEG C of dry 15h.Product is tested through XRD, meets JCPDS standard cards 6-0344
Cuprous chloride crystal standard diagram.
Embodiment 5
By 0.01mol Cu (OAc)2·H2O is dissolved in 250mL water, in 25 DEG C and 1500-2000r/min of stirring speed
The 0.02mol hydroxylamine hydrochloride aqueous solution is added dropwise under rate（3mL）, time for adding control is in 5-10min；After adding, continue to stir
40min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the stannous chloride of white in 60 DEG C of dry 20h.Product
Tested through XRD, meet the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 6
By 0.01mol Cu (OAc)2·H2O is dissolved in 300mL water, in 25 DEG C and 1500-2000r/min of stirring speed
The 0.05mol hydroxylamine hydrochloride aqueous solution is added dropwise under rate（4mL）, time for adding control is in 5-10min；After adding, continue to stir
40min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the stannous chloride of white in 70 DEG C of dry 20h.Product
Tested through XRD, meet the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 7
By 0.01mol CuCl2·2H2O and 0.01molNaOAc is dissolved in 5mL water, in 25 DEG C and 1500-2000r/
The 0.001mol hydroxylamine hydrochloride aqueous solution is added dropwise under min stir speed (S.S.)（2mL）, time for adding control is in 1-5min；After adding, after
Continuous stirring 20min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the protochloride of white in 70 DEG C of dry 10h
Copper.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 8
By 0.01mol CuCl2·2H2O and 0.02mol NaOAc are dissolved in 50mL water, in 25 DEG C and 1500-2000r/
The 0.02mol hydroxylamine hydrochloride aqueous solution is added dropwise under min stir speed (S.S.)（3mL）, time for adding control is in 1-5min；After adding, after
Continuous stirring 20min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the protochloride of white in 60 DEG C of dry 20h
Copper.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 9
By 0.01mol CuCl2·2H2O and 0.03mol NaOAc are dissolved in 100mL water, in 15 DEG C and 1500-
The 0.02mol hydroxylamine hydrochloride aqueous solution is added dropwise under 2000r/min stir speed (S.S.)（2mL）, time for adding control is in 1-5min；Add
Afterwards, continue to stir 20min, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains the chlorine of white in 70 DEG C of dry 10h
Change cuprous.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 10
By 0.01mol CuBr2It is dissolved in 0.01mol NaOAc in 5mL water, in 25 DEG C and 1500-2000r/min
The 0.005mol hydroxylamine hydrochloride aqueous solution is added dropwise under stir speed (S.S.)（2mL）, time for adding control is in 1-5min；After adding, continue to stir
20min is mixed, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains the stannous chloride of white in 70 DEG C of dry 10h.Production
Product are tested through XRD, meet the standard diagram of JCPDS standard cards 6-0344 chlorination copper crystal.
Embodiment 11
By 0.01mol CuBr2It is dissolved in 0.02mol NaOAc in 50mL water, in 25 DEG C and 1500-2000r/min
The 0.04mol hydroxylamine hydrochloride aqueous solution is added dropwise under stir speed (S.S.)（2mL）, time for adding control is in 1-10min；After adding, continue to stir
20min is mixed, is centrifuged, washing, is placed in vacuum drying chamber and obtains the stannous chloride of white in 70 DEG C of dry 10h.Product passes through
XRD is tested, and meets the standard diagram of JCPDS standard cards 6-0344 chlorination copper crystal.
Embodiment 12
By 0.01mol Cu (NO3)2·3H2O and 0.01mol NaOAc are dissolved in 5mL water, in 25 DEG C and 1500-
The 0.005mol hydroxylamine hydrochloride aqueous solution is added dropwise under 2000r/min stir speed (S.S.)（2mL）, time for adding control is in 1-5min；Add
After complete, continue to stir 20min, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains white in 70 DEG C of dry 10h
Stannous chloride.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 13
By 0.01mol Cu (NO3)2·3H2O and 0.03mol NaOAc are dissolved in 100mL water, in 15 DEG C and 1500-
The 0.02mol hydroxylamine hydrochloride aqueous solution is added dropwise under 2000r/min stir speed (S.S.)（5mL）, time for adding control is in 5-10min；Add
After complete, continue to stir 20min, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains white in 70 DEG C of dry 10h
Stannous chloride.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 14
By 0.01mol Cu (NO3)2·3H2O and 0.02mol NaOAc are dissolved in 50mL water, in 25 DEG C and 1500-
The 0.04mol hydroxylamine hydrochloride aqueous solution is added dropwise under 2000r/min stir speed (S.S.)（5mL）, time for adding control is in 5-10min；Add
After complete, continue to stir 20min, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains white in 70 DEG C of dry 10h
Stannous chloride.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 15
By 0.01mol CuSO4·5H2O and 0.01mol NaOAc are dissolved in 5mL water, in 25 DEG C and 1500-2000r/
The 0.005mol hydroxylamine hydrochloride aqueous solution is added dropwise under min stir speed (S.S.)（2mL）, time for adding control is in 1-5min；After adding, after
Continuous stirring 20min, centrifugation, washing, alcohol are washed, are placed in vacuum drying chamber and obtain the protochloride of white in 70 DEG C of dry 10h
Copper.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment 16
By 0.01mol CuSO4·5H2O and 0.01mol NaOAc are dissolved in 20mL water, in 25 DEG C and 1000-1500r/
The 0.03mol hydroxylamine hydrochloride aqueous solution is added dropwise under min stir speed (S.S.)（5mL）, time for adding control is in 5-10min；After adding,
Continue to stir 20min, centrifugation, washing, alcohol are washed, is placed in vacuum drying chamber and obtains the chlorination of white in 60 DEG C of dry 10h
It is cuprous.Product is tested through XRD, meets the standard diagram of JCPDS standard cards 6-0344 cuprous chloride crystal.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (7)
1. a kind of green synthesis method of stannous chloride, it is characterised in that concretely comprise the following steps：By soluble cupric salt and acetic acid
Sodium is soluble in water, and the reducing agent hydroxylamine hydrochloride aqueous solution is added under conditions of 15-25 DEG C of stirring or hydroxylamine hydrochloride solid is carried out instead
Should, centrifugation, washing, alcohol are washed and are dried in vacuo to obtain target product stannous chloride after reacting completely, wherein soluble cupric salt
For CuCl2·2H2O、CuBr2、Cu(NO3)2·3H2O or CuSO4·5H2O, the mol ratio of soluble cupric salt and hydroxylamine hydrochloride
For 1:0.1-4.
2. the green synthesis method of stannous chloride according to claim 1, it is characterised in that：Described sodium acetate with it is solvable
The mol ratio of property cupric salt is 1-3:1.
3. a kind of green synthesis method of stannous chloride, it is characterised in that concretely comprise the following steps：Soluble cupric salt is dissolved in water
In, add the reducing agent hydroxylamine hydrochloride aqueous solution in 5-30 DEG C or hydroxylamine hydrochloride solid is reacted, centrifugation, water after reacting completely
Wash, alcohol is washed and is dried in vacuo to obtain target product stannous chloride, wherein soluble cupric salt is Cu (OAc)2·H2O, it is soluble
The mol ratio of cupric salt and hydroxylamine hydrochloride is 1:0.5-5.
4. the green synthesis method of the stannous chloride according to claim 1 or 3, it is characterised in that：Described aqueous solvent
Dosage is that the volume that 1mmol solubility cupric salts correspond to water is 0.5-30mL.
5. the green synthesis method of the stannous chloride according to claim 1 or 3, it is characterised in that：Add reducing agent hydrochloric acid
It is 250-2000r/min that stir speed (S.S.) is controlled during aqueous hydroxylamine solution or hydroxylamine hydrochloride solid, adds reducing agent hydrochloric acid hydroxyl
The time control of amine aqueous solution is in 1-10min.
6. the green synthesis method of the stannous chloride according to claim 1 or 3, it is characterised in that：Add reducing agent hydrochloric acid
The reaction time that aqueous hydroxylamine solution or hydroxylamine hydrochloride solid are reacted is 5-30min.
7. the green synthesis method of the stannous chloride according to claim 1 or 3, it is characterised in that：Described vacuum drying
Temperature be 25-70 DEG C, vacuum drying time 10-20h.
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| CN111170828B (en) * | 2020-01-17 | 2023-01-03 | 浙江大学宁波理工学院 | Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst |
| CN114349040A (en) * | 2022-01-18 | 2022-04-15 | 西南大学 | Method for preparing CuCl nanoparticles simply and conveniently without template and application |
| CN114378300B (en) * | 2022-01-21 | 2023-10-20 | 重庆科技学院 | Method for preparing nanometer copper powder by taking copper oxide as raw material |
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| CN103506117A (en) * | 2012-06-20 | 2014-01-15 | 苏州科技学院 | Preparation method of nano cuprous oxide photocatalyst |
| CN103482676A (en) * | 2013-09-29 | 2014-01-01 | 河南师范大学 | Green preparation method of cuprous chloride |
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