CN108689896A - A method of producing thiocarbamide using cyanamide bits - Google Patents
A method of producing thiocarbamide using cyanamide bits Download PDFInfo
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- CN108689896A CN108689896A CN201810658751.0A CN201810658751A CN108689896A CN 108689896 A CN108689896 A CN 108689896A CN 201810658751 A CN201810658751 A CN 201810658751A CN 108689896 A CN108689896 A CN 108689896A
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- China
- Prior art keywords
- thiocarbamide
- cyanamide
- reaction
- lime nitrogen
- bits
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/02—Thiourea
Abstract
The invention belongs to field of inorganic chemical engineering, more particularly to a kind of method producing thiocarbamide using cyanamide bits, this method is using the solid waste generated in cyanamide industrial production as primary raw material, lime nitrogen is generated under high temperature with urea reaction, and then is reacted with water, hydrogen sulfide under the action of calcium sulfhydrate and generates thiocarbamide target product.The thiocarbamide production method that the present invention designs, while cyanamide bits value is melted hair, is turned waste into wealth, pass through the change of feed way, thiocarbamide yield is improved to 97% or more, thiocarbamide product index reaches high-class product standard, and a kind of cost-effective approach is provided for the recycling of cyanamide bits and the preparation of thiocarbamide.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, and in particular to a method of producing thiocarbamide using cyanamide bits.
Background technology
1. thiocarbamide is summarized
Thiocarbamide is the important source material in medicine, pesticide synthesis.Also be used as the vulcanization accelerator of rubber, metalliferous mineral it is floating
Select agent, phthalic anhydride processed and fumaric acid catalyst, and be used as metal antirusting agent.In terms of photographic material, it can make
For developer and toner.It can be additionally used in electroplating industry.Thiocarbamide is additionally operable to diazo sensitized paper, synthetic resin coating, anion and hands over
Change many aspects such as resin, germination stimulants, fungicide.Thiocarbamide is also used as fertilizer application.
Main process route is at present:Using lime nitrogen as raw material, part lime nitrogen is added at a lower temperature and leads to sulphur
Change hydrogen to be absorbed, after absorption reaches a certain amount of, then carries out lime nitrogen secondary batching temperature reaction.This method is due to absorber portion temperature
Spend it is relatively low, lime nitrogen hydrolysis again it is very fast, cause a large amount of side reactions (such as dicyandiamide) occur, to reduce the product of thiocarbamide technique
Yield.
2. cyanamide is summarized
The mode of production of industrial cyanamide is at present:Using lime nitrogen as raw material, in water and carbon dioxide under the action of system
Standby cyanamide, while a large amount of calcium carbonate bits are generated, cause larger pressure to environmental protection.
Invention content
In view of the deficiencies of the prior art, the present invention is directed to existing cyanamide bits calcium carbonate is prepared into calcium cyanamide, again
Further reaction prepares thiocarbamide, eliminates the pollution of cyanamide bits, while realized value melts hair, sulphur is prepared by change
Urea hydrogen sulfide absorption section temperature, improves the yield of thiocarbamide, improves the quality of thiocarbamide product.
The invention is realized in this way:Using the solid waste generated in cyanamide industrial production as primary raw material, under high temperature with urine
Element reaction generates lime nitrogen, and then is reacted with water, hydrogen sulfide under the action of calcium sulfhydrate and generate thiocarbamide target product.Including with
Lower step:
(1) preparation of lime nitrogen:It is ground after cyanamide Industrial Solid Waste is mixed with urea, 300-400 DEG C under nitrogen protection
After lower calcining 2-3h, it is warming up to 700-800 DEG C and continues to calcine 2-3h, be cooled to room temperature under nitrogen atmosphere after reaction, by institute
Lime nitrogen crude product is obtained to be ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in water, is warming up to 60-90 DEG C, it is primary that lime nitrogen crude product is added portionwise
Material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 0.5-1h, and lime nitrogen crude product secondary material is added, and continues
Insulation reaction 2.5-3h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product is obtained by filtration,
Mother liquid recycle.
The Industrial Solid Waste is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent is water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):2-6.
Inventor has found during the experiment:The addition of one defective material of lime nitrogen crude product is reaction dissolvent matter in step (2)
The 1/18 of amount can obtain preferable result when the addition of lime nitrogen crude product secondary material is the 1/6 of reaction dissolvent quality.
In the present invention, lime nitrogen crude product will be added in two portions.Because the preparation of thiocarbamide is specifically divided into two stages, first, inhaling
The receipts stage, second is that holding stage.Absorption stage main purpose is to absorb enough hydrogen sulfide to have sulphur at this point, product is more complicated
Calcium hydride, thiocarbamide, cyanamide etc..The key reaction of generation has:1. lime nitrogen is hydrolyzed into calcium hydroxide and cyanamide.2. cyanamide
It is reacted with calcium sulfhydrate and generates thiocarbamide.3. cyanamide self-polymerization is at dicyandiamide.4. calcium hydroxide is reacted with hydrogen sulfide generates sulphur
Calcium hydride realizes that hydrogen sulfide is fixed.There is cyanamide at this time and aggregates into dicyandiamide and cyanamide and calcium sulfhydrate generation thiocarbamide
The speed of competitive reaction, 60 DEG C or less generation thiocarbamides is slower, generates the speed of dicyandiamide, side reaction is caused to aggravate, seriously
Influence product yield and quality.Second stage key reaction be calcium sulfhydrate react with cyanamide generation thiocarbamide and calcium hydroxide,
Calcium sulfhydrate is reacted with lime nitrogen generates thiocarbamide and calcium hydroxide.
The present invention carries absorption stage reaction temperature to 60-90 DEG C, has the advantage that:1. it is secondary anti-to inhibit dicyandiamide to generate
It answers.2. thiocarbamide generates quick, reaction time reduction.3. thiocarbamide yield is improved to 97%, thiocarbamide quality reaches high-class product level.
In conclusion existing cyanamide bits calcium carbonate is prepared by the present invention, lime nitrogen crude product, further reaction is made
Standby thiocarbamide eliminates the pollution of cyanamide bits, while realized value melts hair, prepares thiourea cure hydrogen by change and absorb
Duan Wendu controls the generation of side reaction, reduces impurity, improves the yield of thiocarbamide, improves the quality of thiocarbamide product.
Mother liquor of the present invention total recovery after 6 times are applied mechanically is more than 97%, and thiocarbamide product reaches high-class product standard.
Specific implementation mode:
Embodiment 1
A method of producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at lower 300 DEG C of nitrogen protection
After burning 3h, it is warming up to 800 DEG C and continues to calcine 2h, be cooled to room temperature under nitrogen atmosphere after reaction, by gained lime nitrogen crude product
It is ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 60 DEG C, lime nitrogen crude product is added portionwise
One defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 0.5h, and lime nitrogen crude product secondary material is added, after
Continuous insulation reaction 3h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product is obtained by filtration, female
Liquid is applied mechanically.
The Industrial Solid Waste calcium carbonate is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent
For water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):3.
The addition of one defective material of lime nitrogen is the 1/18 of water (being mother liquor after mother liquid recycle) quality in step (2), secondary material
Addition be the 1/6 of water (being mother liquor after mother liquid recycle) quality.
Temperature is 15 DEG C after cooling in step (2);
Total recovery is up to 97.3% after 6 times are applied mechanically for mother liquor, and thiocarbamide product content is more than 99%, and other indexs reach
High-class product standard.
Embodiment 2
A method of producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at lower 400 DEG C of nitrogen protection
After burning 2.5h, it is warming up to 700 DEG C and continues to calcine 3h, be cooled to room temperature under nitrogen atmosphere after reaction, gained lime nitrogen is thick
Product are ground, are spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 90 DEG C, lime nitrogen crude product is added portionwise
One defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 1h, and lime nitrogen crude product secondary material is added, and continues
Insulation reaction 2.8h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product is obtained by filtration, female
Liquid is applied mechanically.
The Industrial Solid Waste calcium carbonate is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent
For water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):2.
The addition of one defective material of lime nitrogen is the 1/18 of water (being mother liquor after mother liquid recycle) quality in step (2), secondary material
Addition be the 1/6 of water (being mother liquor after mother liquid recycle) quality.
Temperature is 14 DEG C after cooling in step (2);
Total recovery is up to 97.1% after 6 times are applied mechanically for mother liquor, and thiocarbamide product content is more than 99%, and other indexs reach
High-class product standard.
Embodiment 3
A method of producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at lower 350 DEG C of nitrogen protection
After burning 2.2h, it is warming up to 750 DEG C and continues to calcine 2.5h, be cooled to room temperature under nitrogen atmosphere after reaction, by gained lime nitrogen
Crude product is ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 70 DEG C, lime nitrogen crude product is added portionwise
One defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 0.8h, and lime nitrogen crude product secondary material is added, after
Continuous insulation reaction 3h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product is obtained by filtration, female
Liquid is applied mechanically.
The Industrial Solid Waste calcium carbonate is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent
For water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):4.
The addition of one defective material of lime nitrogen is the 1/18 of water (being mother liquor after mother liquid recycle) quality in step (2), secondary material
Addition be the 1/6 of water (being mother liquor after mother liquid recycle) quality.
Temperature is 16 DEG C after cooling in step (2);
Total recovery is up to 97.8% after 6 times are applied mechanically for mother liquor, and thiocarbamide product content is more than 99%, and other indexs reach
High-class product standard.
Embodiment 4
A method of producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at lower 330 DEG C of nitrogen protection
After burning 3h, it is warming up to 800 DEG C and continues to calcine 2h, be cooled to room temperature under nitrogen atmosphere after reaction, by gained lime nitrogen crude product
It is ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 80 DEG C, lime nitrogen crude product is added portionwise
One defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 1h, and lime nitrogen crude product secondary material is added, and continues
Insulation reaction 3h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product, mother liquor is obtained by filtration
It applies mechanically.
The Industrial Solid Waste calcium carbonate is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent
For water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):5.
The addition of one defective material of lime nitrogen is the 1/18 of water (being mother liquor after mother liquid recycle) quality in step (2), secondary material
Addition be the 1/6 of water (being mother liquor after mother liquid recycle) quality.
Temperature is 15 DEG C after cooling in step (2);
Total recovery is up to 97.5% after 6 times are applied mechanically for mother liquor, and thiocarbamide product content is more than 99%, and other indexs reach
High-class product standard.
Embodiment 5
A method of producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at lower 380 DEG C of nitrogen protection
After burning 2h, it is warming up to 800 DEG C and continues to calcine 3h, be cooled to room temperature under nitrogen atmosphere after reaction, by gained lime nitrogen crude product
It is ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 90 DEG C, lime nitrogen crude product is added portionwise
One defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 1h, and lime nitrogen crude product secondary material is added, and continues
Insulation reaction 2.5h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide product is obtained by filtration, female
Liquid is applied mechanically.
The Industrial Solid Waste calcium carbonate is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent
For water.
With the molar ratio computing of pure material, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):6.
The addition of one defective material of lime nitrogen is the 1/18 of water (being mother liquor after mother liquid recycle) quality in step (2), secondary material
Addition be the 1/6 of water (being mother liquor after mother liquid recycle) quality.
Temperature is 15 DEG C after cooling in step (2);
Total recovery is up to 97.6% after 6 times are applied mechanically for mother liquor, and thiocarbamide product content is more than 99%, and other indexs reach
High-class product standard.
Claims (6)
1. a kind of method producing thiocarbamide using cyanamide bits, which is characterized in that include the following steps:
(1) preparation of lime nitrogen:It grinds after cyanamide Industrial Solid Waste is mixed with urea, is forged at 300-400 DEG C under nitrogen protection
After burning 2-3h, it is warming up to 700-800 DEG C and continues to calcine 2-3h, be cooled to room temperature under nitrogen atmosphere after reaction, by gained stone
Grey nitrogen crude product is ground, is spare;
(2) prepared by thiocarbamide:It is continually fed into hydrogen sulfide in reaction dissolvent, is warming up to 60-90 DEG C, lime nitrogen crude product one is added portionwise
Defective material is stirred to react, and the completion that feeds intake stops ventilation after continuing ventilation insulation reaction 0.5-1h, and lime nitrogen crude product secondary material is added, after
Continuous insulation reaction 2.5-3h;Reaction terminates, and filters while hot, and gained filtrate cooling, thiocarbamide product is precipitated, and thiocarbamide production is obtained by filtration
Product, mother liquid recycle.
2. a kind of method producing thiocarbamide using cyanamide bits according to claim 1, which is characterized in that the work
Industry solid waste is the solid waste calcium carbonate generated in cyanamide industrial production;The reaction dissolvent is water.
3. a kind of method producing thiocarbamide using cyanamide bits according to claim 1, which is characterized in that with pure material
Molar ratio computing, the ratio of the amount of the substance of calcium carbonate and urea is 1 in step (1):2-6.
4. a kind of method producing thiocarbamide using cyanamide bits according to claim 1, which is characterized in that step (2)
Middle reaction temperature is 80 DEG C.
5. a kind of method producing thiocarbamide using cyanamide bits according to claim 1, which is characterized in that step (2)
The addition of middle one defective material of lime nitrogen crude product is the 1/18 of reaction dissolvent quality, and the addition of lime nitrogen crude product secondary material is reaction
The 1/6 of solvent quality.
6. a kind of method producing thiocarbamide using cyanamide bits according to claim 1, which is characterized in that step (2)
The temperature of middle sulfocarbamide crystallization is 14 ± 2 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810658751.0A CN108689896A (en) | 2018-06-25 | 2018-06-25 | A method of producing thiocarbamide using cyanamide bits |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810658751.0A CN108689896A (en) | 2018-06-25 | 2018-06-25 | A method of producing thiocarbamide using cyanamide bits |
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| CN201810658751.0A Pending CN108689896A (en) | 2018-06-25 | 2018-06-25 | A method of producing thiocarbamide using cyanamide bits |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279795A (en) * | 2020-10-26 | 2021-01-29 | 山东益丰生化环保股份有限公司 | Method for continuously producing thiourea by using microchannel reactor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143938A (en) * | 1994-03-11 | 1997-02-26 | Skw特罗斯特贝格股份公司 | Process for preparing calcium cyanamide from urea |
-
2018
- 2018-06-25 CN CN201810658751.0A patent/CN108689896A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143938A (en) * | 1994-03-11 | 1997-02-26 | Skw特罗斯特贝格股份公司 | Process for preparing calcium cyanamide from urea |
Non-Patent Citations (1)
| Title |
|---|
| 毕慧峰等: "以炼厂硫化氢为原料生产硫脲的试验及可能性研究", 《当代化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279795A (en) * | 2020-10-26 | 2021-01-29 | 山东益丰生化环保股份有限公司 | Method for continuously producing thiourea by using microchannel reactor |
| CN112279795B (en) * | 2020-10-26 | 2022-12-09 | 益丰新材料股份有限公司 | Method for continuously producing thiourea by using microchannel reactor |
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Application publication date: 20181023 |