CN110818604A - Synthetic method of thiourea - Google Patents
Synthetic method of thiourea Download PDFInfo
- Publication number
- CN110818604A CN110818604A CN201911186153.9A CN201911186153A CN110818604A CN 110818604 A CN110818604 A CN 110818604A CN 201911186153 A CN201911186153 A CN 201911186153A CN 110818604 A CN110818604 A CN 110818604A
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- CN
- China
- Prior art keywords
- thiourea
- reaction
- catalyst
- charcoal powder
- ammonium sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 14
- 239000003610 charcoal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LBVNUQQORDPZCR-UHFFFAOYSA-N calcium;sulfane Chemical compound S.[Ca] LBVNUQQORDPZCR-UHFFFAOYSA-N 0.000 description 1
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing thiourea, which takes charcoal powder and ammonium sulfide as raw materials to synthesize a target product thiourea under the action of a catalyst. The method has the advantages of simple operation steps, low energy consumption, short production period and high product yield and purity, meets the quality requirements of the market on the thiourea, and greatly reduces the production cost on the premise of ensuring the product yield and quality.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a synthetic method of thiourea.
Background
Thiourea, which is used as a raw material for synthesizing medicines such as sulfathiazole, methionine, pig fattening tablets and the like. Used as raw materials of dye, dyeing assistant, resin and molding powder. It can also be used as flotation agent for metal mineral, catalyst for preparing phthalic anhydride and fumaric acid, and as metal rust inhibitor. Thiourea is also used as a fertilizer.
The prior art is that hydrogen sulfide gas is absorbed by lime milk under negative pressure to prepare calcium hydrogen sulfide solution, then the solution reacts with calcium cyanamide, the molar ratio of calcium hydrosulfide to calcium cyanamide is 1: 5, the reaction temperature is (80 +/-5) DEG C under continuous stirring, the reaction time is 3h, thiourea liquid can be generated by negative pressure filtration, and then the crystal thiourea is obtained by evaporation, filtration, cooling and crystallization, and the finished product is obtained by centrifugal dehydration and drying. The raw material calcium cyanamide belongs to a high-energy-consumption product, and a large amount of black solid waste residue can be generated after thiourea is produced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synthetic method of thiourea, which solves the problems of high production cost, large energy consumption, large pollution and the like in the prior art.
The synthesis method of the thiourea takes charcoal powder and ammonium sulfide as raw materials, and synthesizes the target product thiourea under the action of a catalyst, wherein the reaction equation is as follows:
the catalyst is one or more of silicic acid, aluminum oxide or zinc oxide.
The charcoal powder: ammonium sulfide: the molar ratio of the catalyst is 1: 0.7-1.3: 0.01-0.05.
The preparation method comprises the following specific steps:
(1) pouring charcoal powder and ammonium sulfide into a reactor, adding a catalyst, and introducing nitrogen for protection;
(2) heating to a reaction temperature, pressurizing to a certain pressure by using nitrogen gas, and reacting for a period of time;
(3) after the reaction is finished, decompressing, cooling to room temperature and taking out the solid;
(4) dissolving the solid with water, filtering, and cooling and crystallizing the filtrate to obtain the thiourea product.
The reaction temperature is 200-400 ℃, the reaction time is 2-15h, and the reaction pressure is 0.5-10 Mpa.
The thiourea synthesis method adopted by the invention uses solid raw materials in the reaction, is not limited by regions, is safer than hydrogen sulfide gas in solid, fully utilizes ammonium sulfide generated by the reaction of hydrogen sulfide and ammonia gas generated in the petrochemical production process, and also reduces the treatment cost of toxic gas in waste gas. In addition, the combustible gas produced by the reaction can provide heat, and the cost is further reduced. And nitrogen is introduced in the reaction process to prevent oxygen in the air from entering, so that the charcoal powder is oxidized. The reaction temperature is set to be beneficial to reducing energy consumption and side reaction and improving the yield of the target product, if the reaction temperature is too low, the reaction can not be carried out, if the reaction temperature is too high, the energy consumption is increased, side reaction is generated, and the yield of the target product is reduced by the generated by-product. The reaction time is limited, so that the reaction can be fully performed, the energy consumption for reaction can be reduced as far as possible, the reaction can be insufficient due to short reaction time, and the energy consumption can be obviously improved due to long reaction time. The reaction is carried out under increased pressure, which is lower than 0.5MPa, and the reaction basically does not occur, and the higher pressure brings higher cost to the equipment.
In conclusion, the beneficial effects of the invention are as follows:
(1) the method has the advantages of simple operation steps, low energy consumption, short production period and high product yield and purity, and meets the quality requirements of the market on the thiourea;
(2) the raw materials are solid, so that potential safety hazards are reduced;
(3) the solid catalyst is simple to recover and can be repeatedly used.
The invention greatly reduces the production cost on the premise of ensuring the product yield and quality.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.
Example 1
Charcoal powder and ammonium sulfide are used as raw materials, and a target product thiourea is synthesized under the action of a catalyst, wherein the reaction equation is as follows:
the method comprises the following specific steps:
(1) pouring 12g of charcoal powder and 47.6g of ammonium sulfide into a reactor, adding 0.8g of catalyst zinc oxide, and introducing nitrogen for protection;
(2) heating to 200 ℃, pressurizing to 0.5Mpa by using nitrogen gas for reaction for 2 hours;
(3) after the reaction is finished, decompressing, cooling to room temperature and taking out the solid;
(4) dissolving the solid with water, filtering, and cooling and crystallizing the filtrate to obtain 75.64g of thiourea finished product.
The product purity is 99.0 percent, and the product yield is 96.0 percent.
Example 2
Charcoal powder and ammonium sulfide are used as raw materials, and a target product thiourea is synthesized under the action of a catalyst, wherein the reaction equation is as follows:
the method comprises the following specific steps:
(1) pouring 12g of charcoal powder and 88.4g of ammonium sulfide into a reactor, adding 1.1g of catalyst alumina, and introducing nitrogen for protection;
(2) heating to 400 ℃, pressurizing to 10Mpa by using nitrogen gas for reaction, and reacting for 15 h;
(3) after the reaction is finished, decompressing, cooling to room temperature and taking out the solid;
(4) dissolving the solid with water, filtering, and cooling and crystallizing the filtrate to obtain 74.77g of thiourea finished product.
The product purity is 99.1 percent, and the product yield is 95.0 percent.
Example 3
Charcoal powder and ammonium sulfide are used as raw materials, and a target product thiourea is synthesized under the action of a catalyst, wherein the reaction equation is as follows:
the method comprises the following specific steps:
(1) pouring 12g of charcoal powder and 74.3g of ammonium sulfide into a reactor, adding 1g of catalyst silicic acid, and introducing nitrogen for protection;
(2) heating to 350 deg.C, pressurizing to 7.5Mpa with nitrogen, and reacting for 8 h;
(3) after the reaction is finished, decompressing, cooling to room temperature and taking out the solid;
(4) dissolving the solid with water, filtering, and cooling and crystallizing the filtrate to obtain 76.82g of thiourea finished product.
The product purity is 99.5 percent, and the product yield is 98.0 percent.
Claims (6)
1. A method for synthesizing thiourea is characterized in that: charcoal powder and ammonium sulfide are used as raw materials, and a target product thiourea is synthesized under the action of a catalyst, wherein the reaction equation is as follows:
the catalyst is one or more of silicic acid, aluminum oxide or zinc oxide.
2. A method of synthesizing thiourea according to claim 1, wherein: the charcoal powder: ammonium sulfide: the molar ratio of the catalyst is 1: 0.7-1.3: 0.01-0.05.
3. A process for the synthesis of thiourea according to claim 1, characterized by: the method comprises the following specific steps:
(1) pouring charcoal powder and ammonium sulfide into a reactor, adding a catalyst, and introducing nitrogen for protection;
(2) heating to a reaction temperature, pressurizing to a certain pressure by using nitrogen gas, and reacting for a period of time;
(3) after the reaction is finished, decompressing, cooling to room temperature and taking out the solid;
(4) dissolving the solid with water, filtering, and cooling and crystallizing the filtrate to obtain the thiourea product.
4. A method of synthesizing thiourea according to claim 3, wherein: the reaction temperature in the step (2) is 200-400 ℃.
5. A method of synthesizing thiourea according to claim 3, wherein: the reaction time in the step (2) is 2-15 h.
6. A process for the synthesis of thiourea according to claim 3, characterized by: the pressure in the step (2) is 0.5-10 Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911186153.9A CN110818604A (en) | 2019-11-26 | 2019-11-26 | Synthetic method of thiourea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911186153.9A CN110818604A (en) | 2019-11-26 | 2019-11-26 | Synthetic method of thiourea |
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| Publication Number | Publication Date |
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| CN110818604A true CN110818604A (en) | 2020-02-21 |
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|---|---|---|---|
| CN201911186153.9A Pending CN110818604A (en) | 2019-11-26 | 2019-11-26 | Synthetic method of thiourea |
Country Status (1)
| Country | Link |
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| CN (1) | CN110818604A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695672A (en) * | 2010-01-07 | 2012-09-26 | 国际壳牌研究有限公司 | A process for the manufacture of sulphide compounds |
| CN107311903A (en) * | 2017-06-30 | 2017-11-03 | 山东益丰生化环保股份有限公司 | A kind of clean method for preparing of thiocarbamide |
-
2019
- 2019-11-26 CN CN201911186153.9A patent/CN110818604A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695672A (en) * | 2010-01-07 | 2012-09-26 | 国际壳牌研究有限公司 | A process for the manufacture of sulphide compounds |
| CN107311903A (en) * | 2017-06-30 | 2017-11-03 | 山东益丰生化环保股份有限公司 | A kind of clean method for preparing of thiocarbamide |
Non-Patent Citations (6)
| Title |
|---|
| 《化工百科全书》编辑委员会编: "《化工百科全书》", 31 March 1993 * |
| 别洛诺什科 著: "《炼焦化学新产品及工艺》", 30 September 1982 * |
| 熊刚 等: "利伐沙班关键中间体4-（4-氨基苯基）-3-吗啉酮的合成工艺改进", 《化学与生物工程》 * |
| 王九如: "二硫化碳的制造", 《化学世界》 * |
| 罗代暄: "《化学试剂与精细化学品合成基础》", 31 May 1991 * |
| 许戈文 等: "《合成香料产品技术手册》", 29 February 1996 * |
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Application publication date: 20200221 |