CN107963663A - The synthetic method of arsenic trichloride - Google Patents
The synthetic method of arsenic trichloride Download PDFInfo
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- CN107963663A CN107963663A CN201711445229.6A CN201711445229A CN107963663A CN 107963663 A CN107963663 A CN 107963663A CN 201711445229 A CN201711445229 A CN 201711445229A CN 107963663 A CN107963663 A CN 107963663A
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- arsenic
- arsenic trichloride
- synthetic method
- sulfuric acid
- concentrated sulfuric
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/007—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application provides a kind of synthetic method of arsenic trichloride, it includes step：S1, arsenic trioxide is added in concentrated hydrochloric acid, and opening stirring is reacted it, continue to stir and add the concentrated sulfuric acid after reaction until dehydration completely, then stratification in liquid distributing device is placed reaction liquid into, lower floor's liquid is then collected, obtains arsenic trichloride crude product；S2, arsenic trichloride crude product is placed in distilling apparatus, and heating carries out distilation, is collected 130 DEG C~135 DEG C of cut, is obtained the arsenic trichloride liquid of transparent clarification.The synthetic method of the application has the advantages that product purity is high, synthetic yield is high, cost is low, process is easy to control, process stabilizing, equipment requirement are low, is adapted for large-scale industrial production.
Description
Technical field
This application involves materials synthesis field, more particularly to a kind of synthetic method of arsenic trichloride.
Background technology
Arsenic trichloride belongs to inorganic salt product, and alias chlorination arsenous, is colourless or faint yellow smoke oily liquids, opposite point
Son amount is 181.28, and fusing point is -8.5 DEG C, and boiling point is 130.2 DEG C, is dissolved in ethanol, ether, concentrated hydrochloric acid, relative density (water=1g/
ML) it is 2.16g/mL.High-purity arsenical trichloride can be used as semi-conducting material and synthesize the raw material of the organic compound containing arsenic, can also use
In preparing high purity arsenic, or for field of pesticides etc..
At present, the method for producing arsenic trichloride mainly has hydrochloric acid method and chlorine method.
The process that hydrochloric acid method prepares arsenic trichloride is：Arsenic trioxide is added in reactor, concentrated hydrochloric acid is added, is stirring
Mix down and the concentrated sulfuric acid is slowly added dropwise, due to the dropwise addition of the concentrated sulfuric acid, be removed water caused by reaction, the arsenic trichloride of generation occurs
Two-phase laminated flow and be sunken to reactor bottom.After the concentrated sulfuric acid drips off, heating, distillation, the cut of 90 DEG C~107 DEG C of collection.It will distillate
Liquid cools down, and arsenic trichloride (lower floor) is separated with acid layer (upper strata) with separatory funnel, and arsenic trichloride product is made.The method generation
Arsenic trichloride easily hydrolyzes to form arsenious acid during the reaction, causes yield not high, and spent acid yield is bigger, processing cost
It is higher.
The process that chlorine method prepares arsenic trichloride is：Arsenic raw material is fitted into subliming furnace, heating under vacuum makes arsenic
Distillation, the arsenic steam after distillation condense under condensation temperature, obtain purification arsenic；Arsenic after purification is fitted into chlorination furnace, is passed through
Chlorine and heating and chlorine reaction, generate arsenic trichloride；Then arsenic trichloride is passed through in dechlorinator, heats up and steam arsenic trichloride
Go out, the arsenic trichloride steamed is by obtaining removal of impurities arsenic trichloride after dechlorinator's soaking zone；Removal of impurities arsenic trichloride is passed through essence
Evaporate in kettle, by the arsenic trichloride that purification is obtained after rectifying still soaking zone.Since the reaction efficiency of chlorine and arsenic steam is not high,
Cause technological process longer, extend the reaction time, so as to add cost output；In addition, introducing chlorine in reaction, pair set
Standby installation security is more demanding.
The content of the invention
In view of problem present in background technology, the purpose of the application is to provide a kind of synthetic method of arsenic trichloride,
The synthetic method has that product purity is high, synthetic yield is high, cost is low, process is easy to control, process stabilizing, equipment requirement are low
The advantages of, it is adapted for large-scale industrial production.
In order to achieve the above object, in the one side of the application, this application provides a kind of synthetic method of arsenic trichloride,
It includes step：S1, arsenic trioxide is added in concentrated hydrochloric acid, and opening stirring is reacted it, continues to stir after reaction
Mix and add the concentrated sulfuric acid until dehydration completely, then places reaction liquid into stratification in liquid distributing device, then collect subnatant
Body, obtains arsenic trichloride crude product；S2, arsenic trichloride crude product is placed in distilling apparatus, and heating carries out distilation, collects 130
DEG C~135 DEG C of cut, obtain the arsenic trichloride liquid of transparent clarification.
Relative to the prior art, the application's has the beneficial effect that：
The application is reacted using arsenic trioxide and concentrated hydrochloric acid as raw material, is added the concentrated sulfuric acid and is dehydrated, obtains three
Arsenic chloride, by controlling arsenic trioxide, concentrated hydrochloric acid, the dosage of the concentrated sulfuric acid and the concentration of concentrated hydrochloric acid, can be effectively reduced trichlorine
Change arsenic hydrolysis during the reaction, improve the yield and purity of arsenic trichloride, at the same the arsenic trioxide not reacted completely and
The concentrated sulfuric acid after water suction can reuse after processing, reduce waste disposal cost, avoid causing the wasting of resources.
The synthetic method of the application also has that raw material is simple, cost is relatively low, building-up process is easy to control, process stabilizing, sets
It is standby to require the advantages of low, it is adapted for large-scale industrial production.
Embodiment
The following detailed description of the synthetic method of the arsenic trichloride according to the application.
Step is included according to the synthetic method of the arsenic trichloride of the application：S1, arsenic trioxide is added in concentrated hydrochloric acid, is opened
Opening stirring is reacted it, is continued to stir after reaction and is added the concentrated sulfuric acid until dehydration completely, then puts reaction solution
The stratification in liquid distributing device, then collects lower floor's liquid, obtains arsenic trichloride crude product；S2, arsenic trichloride crude product is placed in
In distilling apparatus, heating carries out distilation, collects 130 DEG C~135 DEG C of cut, obtains the arsenic trichloride liquid of transparent clarification
Body.
In the synthetic method of the application, arsenic trioxide is added in concentrated hydrochloric acid and is reacted, then adds the concentrated sulfuric acid
It is dehydrated, takes arsenic trichloride crude product to carry out distilation near the boiling temperature of arsenic trichloride after stratification, this process
On the one hand it can prevent the arsenic trichloride of generation from occurring because the concentration of hydrochloric acid of system is too low by controlling the concentration of concentrated hydrochloric acid
Hydrolysis, improve the yield of arsenic trichloride, on the other hand can also by near arsenic trichloride boiling point distilation make
Arsenic trichloride has higher purity.Meanwhile the supernatant liquor after stratification is based on the concentrated sulfuric acid, and containing a small amount of completely anti-
The arsenic trioxide answered, is recycled and is reused to it using certain method, to reduce the processing cost of waste liquid, kept away
Exempt to cause the wasting of resources.
The synthetic method of the application is with raw material is simple, cost is relatively low, building-up process is easy to control, process stabilizing, equipment
It is required that the advantages of low, be adapted for large-scale industrial production.
In the synthetic method of the application, in step S1, it is preferable that the mass fraction of concentrated hydrochloric acid is 25%~37%, into
Preferably, the mass fraction of concentrated hydrochloric acid is 32% to one step.
In the synthetic method of the application, in step S1, it is preferable that the reaction temperature of arsenic trioxide and concentrated hydrochloric acid is 60
DEG C~80 DEG C, it is further preferred that the reaction temperature of arsenic trioxide and concentrated hydrochloric acid is 60 DEG C.
In the synthetic method of the application, in step S1, it is preferable that the reaction time of arsenic trioxide and concentrated hydrochloric acid is
0.5h~2h, it is further preferred that the reaction time of arsenic trioxide and concentrated hydrochloric acid is 2h.
In the synthetic method of the application, in step S1, it is preferable that arsenic trioxide, concentrated hydrochloric acid, the mass ratio of the concentrated sulfuric acid
For 1:(3.8~4.3):(2.9~4.6), it is further preferred that the mass ratio of arsenic trioxide, concentrated hydrochloric acid, the concentrated sulfuric acid is 1:
(4.0~4.2):(3.6~4.2).
In the synthetic method of the application, in step S1, it is preferable that it is 200rpm to control mixing speed when adding the concentrated sulfuric acid
~500rpm, it is further preferred that it is 300rpm~400rpm to control mixing speed when adding the concentrated sulfuric acid.
,, can be acute in dehydration if the addition speed of the concentrated sulfuric acid is too fast in step S1 in the synthetic method of the application
Strong heat release, can cause the arsenic trichloride hydrolysis of generation, it is preferable that the addition speed of the concentrated sulfuric acid is 400mL/h~600mL/h.
In the synthetic method of the application, in step S1, since the main function of the concentrated sulfuric acid is dehydration, the concentrated sulfuric acid
Mass fraction is bigger, its dehydrating effect is better, it is preferable that and the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, it is further preferred that
The mass fraction of the concentrated sulfuric acid is 98%.
In the synthetic method of the application, in step S1, it is preferable that the concentrated sulfuric acid continue after being added completely into stir 0.5h~
3h, it is further preferred that the concentrated sulfuric acid continues to stir 1h~2h after being added completely into, to ensure that dehydration is complete.
In the synthetic method of the application, in step S2, distillation mode is air-distillation.
With reference to embodiment, the application is expanded on further.It is to be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
1kg arsenic trioxides are dissolved in 3.5L, mass fraction makes it anti-at 60 DEG C in 32% concentrated hydrochloric acid, to open stirring
2h is answered, obtains the solution of transparent clarification, then proceedes to stir and is slowly added to 1.6L, the concentrated sulfuric acid that mass fraction is 98%, it is dense
The rate of addition of sulfuric acid is 500mL/h, mixing speed 300rpm, continues to stir 1h after being added dropwise to complete, then puts reaction solution
2h is stood in liquid distributing device until obvious layering occurs in reaction solution, wherein, supernatant liquor is mixed for concentrated hydrochloric acid and the concentrated sulfuric acid
Liquid is closed, lower floor is oily arsenic trichloride crude product, and lower floor's liquid is released, and collection obtains arsenic trichloride crude product about 720ml, is computed
The yield for learning arsenic trichloride crude product is 85%.
Above-mentioned arsenic trichloride crude product is placed in distilling apparatus, heat temperature raising is distilled after under normal pressure, collects 130 DEG C
Cut between~135 DEG C, obtains the arsenic trichloride liquid 715ml of transparent clarification, and the purity for learning arsenic trichloride after testing is
More than 99.99%, the yield for being computed learning arsenic trichloride is 99.3%.
Embodiment 2
1kg arsenic trioxides are dissolved in 3.5L, mass fraction makes it anti-at 60 DEG C in 32% concentrated hydrochloric acid, to open stirring
2h is answered, obtains the solution of transparent clarification, then proceedes to stir and is slowly added to 2.5L, the concentrated sulfuric acid that mass fraction is 98%, it is dense
The rate of addition of sulfuric acid is 500mL/h, mixing speed 300rpm, continues to stir 1h after being added dropwise to complete, then puts reaction solution
2h is stood in liquid distributing device until obvious layering occurs in reaction solution, wherein, supernatant liquor is mixed for concentrated hydrochloric acid and the concentrated sulfuric acid
Liquid is closed, lower floor is oily arsenic trichloride crude product, and lower floor's liquid is released, and collection obtains arsenic trichloride crude product about 780ml, is computed
The yield for learning arsenic trichloride crude product is 94.9%.
Above-mentioned arsenic trichloride crude product is placed in distilling apparatus, heat temperature raising is distilled after under normal pressure, collects 130 DEG C
Cut between~135 DEG C, obtains the arsenic trichloride liquid 775ml of transparent clarification, and the purity for learning arsenic trichloride after testing is
More than 99.99%, the yield for being computed learning arsenic trichloride is 99.35%.
Embodiment 3
1kg arsenic trioxides are dissolved in 3.4L, mass fraction makes it anti-at 60 DEG C in 32% concentrated hydrochloric acid, to open stirring
2h is answered, obtains the solution of transparent clarification, then proceedes to stir and is slowly added to 2.3L, the concentrated sulfuric acid that mass fraction is 98%, it is dense
The rate of addition of sulfuric acid is 500mL/h, mixing speed 300rpm, continues to stir 1h after being added dropwise to complete, then puts reaction solution
2h is stood in liquid distributing device until obvious layering occurs in reaction solution, wherein, supernatant liquor is mixed for concentrated hydrochloric acid and the concentrated sulfuric acid
Liquid is closed, lower floor is oily arsenic trichloride crude product, and lower floor's liquid is released, and collection obtains arsenic trichloride crude product about 800ml, is computed
The yield for learning arsenic trichloride crude product is 97.3%.
Above-mentioned arsenic trichloride crude product is placed in distilling apparatus, heat temperature raising is distilled after under normal pressure, collects 130 DEG C
Cut between~135 DEG C, obtains the arsenic trichloride liquid 795ml of transparent clarification, and the purity for learning arsenic trichloride after testing is
More than 99.99%, the yield for being computed learning arsenic trichloride is 99.37%.
Comparative example 1
1kg arsenic trioxides are dissolved in 3.4L, mass fraction makes it anti-at 60 DEG C in 32% concentrated hydrochloric acid, to open stirring
2h is answered, obtains the solution of transparent clarification；Then proceed to stir and be slowly added to 2.3L, the concentrated sulfuric acid that mass fraction is 98%, it is dense
The rate of addition of sulfuric acid is 500mL/h, mixing speed 300rpm, continues to stir 1h after being added dropwise to complete；Place reaction liquid into steaming
In distillation unit, heat temperature raising is distilled after under normal pressure, collects 90 DEG C~107 DEG C of cut；Distillate cooling is placed on point
2h is stood in liquid device until there is obvious layering, wherein, supernatant liquor is concentrated hydrochloric acid and the mixed liquor of the concentrated sulfuric acid, and lower floor is
Oily arsenic trichloride, lower floor's liquid is released, and collection obtains arsenic trichloride liquid about 653ml, learns arsenic trichloride after testing
Purity is more than 99%, and the yield for being computed learning arsenic trichloride is 81.6%.
It was found from the test result analysis of embodiment 1-3, the arsenic trichloride of the application synthesis has higher yield, and obtains
The arsenic trichloride arrived has higher purity.In comparative example 1, arsenic trichloride is synthesized using conventional hydrochloric acid method, in concentrated hydrochloric acid
Distilled with the mixture system of the concentrated sulfuric acid, concentrated hydrochloric acid can volatilize in heating process, and the concentration of hydrochloric acid is not in such system
Disconnected to reduce, part arsenic trichloride hydrolyzes in system, reduces the yield of arsenic trichloride；In addition, carried out at 90 DEG C~107 DEG C
Distillation, part hydrochloric acid and moisture can be distilled in distillate, are also resulted in the purity of arsenic trichloride and are reduced.
Claims (10)
1. a kind of synthetic method of arsenic trichloride, it is characterised in that including step：
S1, arsenic trioxide is added in concentrated hydrochloric acid, and opening stirring is reacted it, is continued to stir after reaction and is added
Then the concentrated sulfuric acid places reaction liquid into stratification in liquid distributing device until dehydration completely, then collect lower floor's liquid, obtain three
Arsenic chloride crude product；
S2, arsenic trichloride crude product is placed in distilling apparatus, and heating carries out distilation, collects 130 DEG C~135 DEG C of cut,
Obtain the arsenic trichloride liquid of transparent clarification.
2. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, the quality of concentrated hydrochloric acid
Fraction is 25%~37%, is preferably 32%.
3. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, arsenic trioxide with
The reaction temperature of concentrated hydrochloric acid is 60 DEG C~80 DEG C, is preferably 60 DEG C.
4. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, arsenic trioxide with
The reaction time of concentrated hydrochloric acid is 0.5h~2h, is preferably 2h.
5. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that arsenic trioxide, dense in step S1
Hydrochloric acid, the mass ratio of the concentrated sulfuric acid are 1:(3.8~4.3):(2.9~4.6), are preferably 1:(4.0~4.2):(3.6~4.2).
6. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, when adding the concentrated sulfuric acid
It is 200rpm~500rpm to control mixing speed, is preferably 300rpm~400rpm.
7. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, the addition of the concentrated sulfuric acid
Speed is 400mL/h~600mL/h.
8. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, the quality of the concentrated sulfuric acid
Fraction is more than or equal to 70%, it is preferable that the mass fraction of the concentrated sulfuric acid is 98%.
9. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S1, the concentrated sulfuric acid adds completely
Continue to stir 0.5h~3h after entering, be preferably 1h~2h.
10. the synthetic method of arsenic trichloride according to claim 1, it is characterised in that in step S2, distillation mode is normal
Pressure distillation.
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| CN201711445229.6A CN107963663A (en) | 2017-12-27 | 2017-12-27 | The synthetic method of arsenic trichloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184905A (en) * | 2021-05-12 | 2021-07-30 | 广东先导稀材股份有限公司 | Impurity removing method for arsenic trichloride high-boiling residue |
| CN113830828A (en) * | 2021-10-14 | 2021-12-24 | 广东先导稀材股份有限公司 | Preparation method of high-purity arsenic trichloride |
| CN114105195A (en) * | 2021-12-31 | 2022-03-01 | 红河砷业有限责任公司 | Method for reducing tin content in arsenic trichloride |
| CN114772638A (en) * | 2022-04-25 | 2022-07-22 | 广东先导微电子科技有限公司 | Chloride dewatering and purifying method |
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| CN103184354A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Preparation method of high-purity arsenic |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103184354A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Preparation method of high-purity arsenic |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184905A (en) * | 2021-05-12 | 2021-07-30 | 广东先导稀材股份有限公司 | Impurity removing method for arsenic trichloride high-boiling residue |
| CN113830828A (en) * | 2021-10-14 | 2021-12-24 | 广东先导稀材股份有限公司 | Preparation method of high-purity arsenic trichloride |
| CN114105195A (en) * | 2021-12-31 | 2022-03-01 | 红河砷业有限责任公司 | Method for reducing tin content in arsenic trichloride |
| CN114772638A (en) * | 2022-04-25 | 2022-07-22 | 广东先导微电子科技有限公司 | Chloride dewatering and purifying method |
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Application publication date: 20180427 |