CN106892793A - The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production - Google Patents
The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production Download PDFInfo
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- CN106892793A CN106892793A CN201710095537.4A CN201710095537A CN106892793A CN 106892793 A CN106892793 A CN 106892793A CN 201710095537 A CN201710095537 A CN 201710095537A CN 106892793 A CN106892793 A CN 106892793A
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- Prior art keywords
- methane
- dithiocyano
- bromide
- bromine
- production
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the circulation utilization method of bromine in a kind of production of bactericide dithiocyano-methane.The invention provides the circulation utilization method of bromine in the production of bactericide dithiocyano-methane, generation methylene bromide, bromochloromethane are reacted under the by-product sodium bromide produced in being produced with dithiocyano-methane and dichloromethane high pressure, methylene bromide and bromochloromethane are used as the raw material in dithiocyano-methane production, bromine recycling in whole production process is realized, production cost is reduced.Realize the reuse of bromine.Ju Ti Walk are evaporated for (1) by dithiocyano-methane waste water is produced suddenly, washed away with ethanol and do not react complete sodium sulfocyanate, the filter cake being filtrated to get adds distilled water obtained solution, solution to remove impurity with activated carbon decolorizing, and the filtrate after decolouring boils off Water Sproading sodium bromide；(2) reaction is obtained methane bromide in the sodium bromide of recovery and dichloromethane being put into autoclave, and product obtains methylene bromide, bromochloromethane, can recycle by rectifying.
Description
Technical field
The invention belongs to bactericide technical field.More particularly to a kind of for the production of bactericide dithiocyano-methane
In bromine recycle.
Background technology
Bactericide dithiocyano-methane, is a kind of broad spectrum activity efficient germicide, and mould proof, the seagoing vessel shell of wrapping paper is used for earliest
The prevention and removing of body surface face marine growth.As non-oxidizable broad-spectrum sterilization algicide, to various fungies, algae and bacterium, bag
Including aerobic organism and anaerobic bacteria has good killing effect, be widely used in leather, papermaking, coating, oil secondary recovery with
And the field such as Treatment of Industrial Water, bamboo and wood be mould proof, pesticide synergistic and seed soaking.It is foremost most widely used in the world at present
One of bactericide.
The main of production method report of bactericide dithiocyano-methane has：NALCO companies in 1967 with methylene bromide with
Sodium sulfocyanate or ammonium thiocyanate are synthesized dithiocyano-methane；The Zhang Deqiang of Haijing Group Co., Ltd., Changlu, Tianjin City in 2010
Deng the improvement carried out to this method in Chinese patent CN101906058A, WO2014167560A1 with methanol-water as solvent on
(105g water/56g methyl alcohol), adds methylene bromide 155g and sodium sulfocyanate 150g, in 84 DEG C of reactions after reacting 4h at 74-75 DEG C
3h, adds 35g methyl alcohol after cooling, then adjusts pH value to 6.3 with sodium acid carbonate, and filtration washing dries to obtain product, and yield 79.3% is pure
Degree is more than 99%HPLC.The above method is easy to operate, product advantages of good crystallization, and post processing is easy, but methylene bromide price is high, makes production
High cost.
Chemical Industry Science Co., Ltd of Huiyuan of Nanxiong City reports in 4 atmospheric pressure bars in Chinese patent CN103351319B
Dichloromethane 80% can be obtained dithiocyano-methane in high yield with ammonium thiocyanate at 90 DEG C under part.But two in the case of HTHP
Thiocyanogen methane can occur polymerisation, and product can be tacky, it is difficult to separates, and causes product impure.
The content of the invention
In order to overcome the shortcoming in prior art, the invention provides a kind of method for improving raw material availability, change few
Environmental pollution, can substantially reduce the cost of production dithiocyano-methane.
The method that the present invention solves the recycling of the bromine in the production of bactericide dithiocyano-methane.Its technique is to use two sulphur
Generation methylene bromide is reacted under the by-product sodium bromide produced in cyano group methane production and dichloromethane high pressure, methylene bromide is used as two
Raw material in thiocyanogen methane production, realizes bromine recycling in whole production process, reduces production cost.Realize
Reuse the part of bromine.
Ju Ti Walk are evaporated for (1) by dithiocyano-methane waste water is produced suddenly, are washed away with ethanol and do not react complete thiocyanic acid
Sodium, the filtrate activated carbon decolorizing being filtrated to get, the filtrate after decolouring boils off Water Sproading sodium bromide；(2) sodium bromide that will be reclaimed
Reaction is obtained methane bromide in being put into autoclave with dichloromethane, and product obtains methylene bromide, bromochloromethane by rectifying, can
For preparing dithiocyano-methane.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1：
(1) production dithiocyano-methane waste water 1150g is evaporated with thin film evaporator, 98% is added in the solid for steaming
Ethanol 1000ml, sodium sulfocyanate is dissolved in ethanol during stirring 0.5h makes solid, and filtering solution, filter cake is washed with 50ml98% ethanol respectively
It is secondary, filter the molten ethanol that boils off and obtain sodium sulfocyanate 110g；In filter cake input 1500g distilled water, stirring and dissolving is heated to boiling and is as cold as
85 DEG C, powdered activated carbon 6g is added, be heated to the decolouring 0.5h that seethes with excitement, heat filtering removes activated carbon, and filtrate boils off moisture and obtains
500g sodium bromides
(2) by sodium bromide 400g, dichloromethane 600g water 200g and TBAB 13g input autoclave, open and stir
160 DEG C are mixed and heated to, pressure is 20atm, react 20h, cooling down is released material, uses separatory funnel branch vibration layer,
40 DEG C of dichloromethane 270.1g, 67~70 DEG C of bromochloromethane 249.4g are collected in oil reservoir rectifying, and 95~98 DEG C obtain methylene bromide
160.3g.
(3) water 100g, ethanol 50g, sodium sulfocyanate 208g, methylene bromide 149g, the tetrabutyl are added in 500ml four-hole bottles
Ammonium bromide 3g agitating heatings, 80 DEG C of reaction 5h, cold filtration, filter cake is washed with water, and vacuum drying obtains light yellow product 95.3g, receives
Rate 85.1%, purity 99.1%HPLC.
Embodiment 2：
(1) by sodium bromide 400g, dichloromethane 500g water 200g and TBAB 10g input autoclave, open and stir
140 DEG C are mixed and heated to, pressure is 16atm, react 12h, cooling down is released material, uses separatory funnel branch vibration layer,
40 DEG C of dichloromethane 180.1g, 67~70 DEG C of bromochloromethane 223g are collected in oil reservoir rectifying, and 95~98 DEG C obtain methylene bromide 124.3g.
(2) water 100g, methyl alcohol 50g, sodium sulfocyanate 208g, methylene bromide 138g, the tetrabutyl are added in 500ml four-hole bottles
Ammonium bromide 5g agitating heatings, 75 DEG C of reaction 7h, cold filtration, filter cake is washed with water, and vacuum drying obtains light yellow product 93.1g, receives
Rate 83.41%, purity 98.4%HPLC.
Embodiment 3：
(1) by sodium bromide 400g, dichloromethane 500g water 200g and TBAB 8g input autoclave, stirring is opened
And heating to 120 DEG C, pressure is 8atm, reacts 24h, and cooling down is released material, uses separatory funnel branch vibration layer, oil
40 DEG C of dichloromethane 251.2g, 67~70 DEG C of bromochloromethane 223g are collected in layer rectifying, and 95~98 DEG C obtain methylene bromide 28.3g.
(2) water 100g, ethanol 50g, sodium sulfocyanate 208g, bromochloromethane 110.8g, four fourths are added in 500ml four-hole bottles
Base ammonium bromide 5g agitating heatings, 80 DEG C of reaction 5h, cold filtration, filter cake is washed with water, and vacuum drying obtains light yellow product 83.1g,
Yield 74.3%, purity 97.3%HPLC.
Claims (4)
1. bromine recycles during a kind of bactericide dithiocyano-methane is produced.
2. recycling for bromine according to claim 1 is to react to realize by sodium bromide and dichloromethane.
3. the catalyst that sodium bromide according to claim 2 is used with dichloromethane reaction is quaternary ammonium salt catalyst.
4. circulation utilization method described according to claim 1 is：
(1) production dithiocyano-methane waste water is evaporated, the filter for do not react complete sodium sulfocyanate, be filtrated to get is washed away with ethanol
Cake adds distilled water obtained solution, and solution activated carbon decolorizing, the filtrate after decolouring boils off Water Sproading sodium bromide；
(2) reaction is obtained methane bromide in the sodium bromide of recovery and dichloromethane being put into autoclave, and product is obtained by rectifying
To methylene bromide, bromochloromethane, can recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710095537.4A CN106892793A (en) | 2017-02-22 | 2017-02-22 | The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710095537.4A CN106892793A (en) | 2017-02-22 | 2017-02-22 | The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106892793A true CN106892793A (en) | 2017-06-27 |
Family
ID=59184951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710095537.4A Pending CN106892793A (en) | 2017-02-22 | 2017-02-22 | The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106892793A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507901A (en) * | 1966-12-23 | 1970-04-21 | Nalco Chemical Co | Method for preparing methylene bis (thiocyanate) |
| CN101357877A (en) * | 2008-09-10 | 2009-02-04 | 山东大地盐化集团有限公司 | Method for preparing dibromomethane and methylene chlorobromide by one-pot |
-
2017
- 2017-02-22 CN CN201710095537.4A patent/CN106892793A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507901A (en) * | 1966-12-23 | 1970-04-21 | Nalco Chemical Co | Method for preparing methylene bis (thiocyanate) |
| CN101357877A (en) * | 2008-09-10 | 2009-02-04 | 山东大地盐化集团有限公司 | Method for preparing dibromomethane and methylene chlorobromide by one-pot |
Non-Patent Citations (1)
| Title |
|---|
| 陈峥等: "二硫氰基甲烷循环工艺的研究", 《精细与专用化学品》 * |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170627 |
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| WD01 | Invention patent application deemed withdrawn after publication |