CN113200897A - Novel cyanidation process for synthesizing cartap - Google Patents
Novel cyanidation process for synthesizing cartap Download PDFInfo
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- CN113200897A CN113200897A CN202110302057.7A CN202110302057A CN113200897A CN 113200897 A CN113200897 A CN 113200897A CN 202110302057 A CN202110302057 A CN 202110302057A CN 113200897 A CN113200897 A CN 113200897A
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- monosultap
- cartap
- solution
- dichloroethane
- cyanide
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- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- MBNMHBAJUNHZRE-UHFFFAOYSA-M thiosultap monosodium Chemical compound [Na+].OS(=O)(=O)SCC(N(C)C)CSS([O-])(=O)=O MBNMHBAJUNHZRE-UHFFFAOYSA-M 0.000 claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003463 adsorbent Substances 0.000 claims abstract description 28
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 20
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 20
- 239000010455 vermiculite Substances 0.000 claims abstract description 20
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 44
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 19
- -1 imino disuccinic acid diiron Chemical compound 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- 239000012670 alkaline solution Substances 0.000 claims description 11
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 14
- 229940080260 iminodisuccinate Drugs 0.000 abstract description 4
- 238000005057 refrigeration Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 10
- 238000000746 purification Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960001604 ferrous succinate Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- MSHXTAQSSIEBQS-UHFFFAOYSA-N s-[3-carbamoylsulfanyl-2-(dimethylamino)propyl] carbamothioate;hydron;chloride Chemical compound [Cl-].NC(=O)SCC([NH+](C)C)CSC(N)=O MSHXTAQSSIEBQS-UHFFFAOYSA-N 0.000 description 3
- 239000003139 biocide Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical compound CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/12—Thiocyanates having sulfur atoms of thiocyanate groups bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a novel cyanidation process for synthesizing cartap, which reduces the impurity content of monosultap through an adsorbent, improves the conversion rate of the monosultap and reduces the using amount of sodium cyanide; through the cross-linking of vermiculite and activated carbon powder, then the burning forms a great proportion of deformation, its selective adsorption performance is promoted, at the same time the adsorption capacity to monosultap is reduced; cyanide ions in a cyanidation reaction system can be effectively stabilized through the diiron iminodisuccinate, so that the cyanide ions cannot overflow to form hydrocyanic acid gas, the control condition of the prior art can be reduced, and the energy consumption of cyanidation reaction refrigeration is reduced; meanwhile, the cyanide ion content of the cyanide-containing wastewater is obviously reduced, and the treatment efficiency and safety of the cyanide-containing wastewater are obviously improved.
Description
Technical Field
The invention relates to a cartap synthesis process, in particular to a novel cyanidation process for synthesizing cartap.
Background
Cartap hydrochloride, also known as 1, 3-bis (carbamoylthio) -2-dimethylaminopropane hydrochloride, is a common name for Cartap hydrochloride. Cartap is a nereistoxin insecticide, has the characteristics of broad spectrum, high efficiency, low toxicity and the like, and is widely used for preventing and treating pests of various crops such as rice, vegetables, fruit trees and the like. In the times of increasingly strong environmental protection concept and health concept, cartap is more and more valued due to the low-toxicity characteristic of cartap.
In the prior art, the synthesis of the single borer killing agent mainly takes monosultap as a raw material and prepares the single borer killing agent after cyanidation reaction and hydrolysis reaction.
Wherein, the cyanidation reaction stage is to dissolve monosultap in dichloroethane, and dropwise add sodium cyanide alkaline solution under refrigeration condition to prepare thiocyanide, and the reaction principle is as follows:
wherein the theoretical molar ratio of the monosultap to the sodium cyanide is 1: 2.
However, in general, in order to ensure the completion of monosultap reaction, the amount of sodium cyanide is required to be excessive, which is generally 2.05-2.1 times of the molar amount of monosultap. However, the process results in excessive sodium cyanide, and wastewater containing sodium cyanide is formed after the reaction is completed, and sodium cyanide and hydrocyanic acid generated after sodium cyanide acidification are all extremely toxic substances.
Meanwhile, the general purity of the monosultap is about 95 percent, the residual impurities can influence the conversion rate of cyanidation reaction, the utilization rate of the monosultap is low, sodium cyanide is excessively consumed, the concentration of cyanide in the wastewater containing the sodium cyanide reaches about 5000mg/L, raw materials are wasted, and the high-concentration cyanide wastewater is a great dangerous source.
Therefore, a novel cyanidation process for synthesizing cartap is required to be developed, the consumption of raw materials is reduced, and cyanide ions in a water phase are stabilized.
Disclosure of Invention
The invention develops a novel cyaniding process for synthesizing cartap, which can effectively reduce the consumption of raw materials and stabilize cyanide ions in a water phase.
A novel cyanidation process for synthesizing cartap comprises the following specific steps:
(1) dissolving monosultap in dichloroethane, adding adsorbent to remove impurities, and making into monosultap dichloroethane solution;
(2) adding alkali into water to adjust the pH value to 8-9, and then dissolving sodium cyanide with the molar weight of 1.95-1.98 times that of monosultap in the water to prepare an alkaline solution of the sodium cyanide;
(3) mixing imino disuccinic acid and ferrous salt according to the molar ratio of 1:2, and adjusting the pH value to 7-8 to prepare an imino disuccinic acid diiron solution;
(4) mixing the imino di-succinic acid di-iron solution with the monosultap dichloroethane solution, stirring and mixing uniformly, cooling to 5-8 ℃,
(5) then dropwise adding an alkaline solution of sodium cyanide, keeping the temperature less than or equal to 10 ℃ in the reaction process, preserving heat for reaction for 2 hours after dropwise adding is finished, and standing for layering after the reaction is finished;
(6) separating the upper water phase to obtain cyanide-containing wastewater; the lower organic phase of thiocyanide is obtained.
Adding water and methanol into the obtained thiocyanide organic phase, introducing hydrogen chloride gas to carry out hydrolysis reaction to obtain cartap solution, and removing solvent and crystallizing to obtain cartap.
Furthermore, the concentration of the monosultap dissolved in the dichloroethane in the step (1) is 4.91 g/L-4.95 g/L.
Further, the ferrous salt in the step (3) is FeCl2Or FeSO4。
Further, after the solution of the imino di-ferrous succinate is mixed into the solution of the monosultap dichloroethane in the step (4), the concentration of the imino di-ferrous succinate is 100 mg/L-120 mg/L.
Further, the purification process of the monosultap in the step (1) is to add active carbon with the mass of 0.5-1% of that of the monosultap, filter the active carbon after adsorption is finished, and prepare the monosultap dichloroethane solution.
Further, the purification process of the monosultap in the step (1) comprises the following steps:
1) dissolving monosultap in dichloroethane to obtain monosultap stock solution;
2) dispersing activated carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare activated carbon slurry;
3) wrapping activated carbon slurry on the surface of vermiculite, coupling and drying, and heating to 300 ℃ by using a muffle furnace to prepare the vermiculite adsorbent;
4) putting the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering to obtain the monosultap dichloroethane solution.
Furthermore, the mass of the activated carbon powder is 0.5-1 percent of the mass of the monosultap, the mass of the KH550 is 3-5 percent of the mass of the activated carbon powder, and the dosage of the vermiculite is 5-10 percent of the mass of the monosultap.
Further, the filtered adsorbent may be washed with water and recrystallized to recover the adsorbed monosultap.
The invention has the advantages that:
1. according to the invention, monosultap is pulped, wherein sodium salt as an impurity and part of organic impurities form a suspension, and the impurity content of monosultap can be effectively reduced through the adsorbent, so that the monosultap conversion rate is improved, and the using amount of sodium cyanide is reduced;
2. according to the invention, vermiculite and activated carbon powder are crosslinked and then are fired to form a great proportion of deformation, so that the selective adsorption performance is improved, and the adsorption capacity of monosultap is reduced; moreover, as the solubility of the monosultap in dichloroethane is lower, about 0.39g/100mL of dichloroethane, the added amount of the adsorbent is very small, and compared with activated carbon, the adsorbent obtained by crosslinking vermiculite and activated carbon powder is very easy to filter and separate;
3. the invention can effectively stabilize cyanide ions in a cyanidation reaction system through the diiron iminodisuccinate so that the cyanide ions cannot form hydrocyanic acid gas to escape; in the prior art, in order to prevent the overflow of the hydrocyanic acid gas, the pH value of a sodium cyanide solution is adjusted to about 10, and the reaction temperature is controlled to be 0-5 ℃, but the invention can reduce the pH value of the sodium cyanide solution, increase the reaction temperature to 10 ℃, and reduce the energy consumption of the refrigeration of the cyanidation reaction;
4. by adding the imino di-ferrous succinate, the treatment efficiency and safety of the cyanide-containing wastewater can be improved.
Detailed Description
Example 1
A novel cyanidation process for synthesizing cartap comprises the following specific steps:
(1) dissolving monosultap in dichloroethane, adding adsorbent to remove impurities, and making into monosultap dichloroethane solution;
(2) adding alkali into water to adjust the pH value to 9, and then dissolving sodium cyanide with the molar weight 1.98 times that of monosultap in the water to prepare an alkaline solution of the sodium cyanide;
(3) mixing imino disuccinic acid and ferrous salt according to the molar ratio of 1:2, and adjusting the pH value to 8.0 to prepare an imino disuccinic acid diiron solution;
(4) mixing the imino di-succinic acid di-iron solution with the monosultap dichloroethane solution, stirring and mixing uniformly, cooling to 5 ℃,
(5) then dropwise adding an alkaline solution of sodium cyanide, keeping the temperature at 8 ℃ in the reaction process, keeping the temperature for reacting for 2 hours after dropwise adding, and standing for layering after the reaction is finished;
(6) separating the upper water phase to obtain cyanide-containing wastewater; the lower organic phase of thiocyanide is obtained.
The concentration of the monosultap dissolved in the dichloroethane in the step (1) is 4.95 g/L.
The ferrous salt in the step (3) is FeSO4。
Mixing the solution of imino di-ferric succinate into the solution of monosultap dichloroethane in the step (4), wherein the concentration of the imino di-ferric succinate is 100 mg/L.
And (2) adding active carbon with the mass of 0.8% of that of the monosultap into the monosultap purification process in the step (1), and filtering the active carbon after adsorption is finished to prepare the monosultap dichloroethane solution.
Example 2
A novel cyanidation process for synthesizing cartap comprises the following specific steps:
(1) dissolving monosultap in dichloroethane, adding adsorbent to remove impurities, and making into monosultap dichloroethane solution;
(2) adding alkali into water to adjust the pH value to 8.5, and then dissolving sodium cyanide with the molar weight of monosultap being 1.96 times that of the monosultap in the water to prepare an alkaline solution of the sodium cyanide;
(3) mixing imino disuccinic acid and ferrous salt according to the molar ratio of 1:2, and adjusting the pH value to 7.7 to prepare an imino disuccinic acid diiron solution;
(4) mixing the imino di-succinic acid di-iron solution with the monosultap dichloroethane solution, stirring and mixing uniformly, cooling to 7 ℃,
(5) then dropwise adding an alkaline solution of sodium cyanide, keeping the temperature at 10 ℃ in the reaction process, keeping the temperature for reaction for 2 hours after dropwise adding, and standing for layering after the reaction is finished;
(6) separating the upper water phase to obtain cyanide-containing wastewater; the lower organic phase of thiocyanide is obtained.
The concentration of the monosultap dissolved in the dichloroethane in the step (1) is 4.92 g/L.
The ferrous salt in the step (3) is FeCl2。
And (4) mixing a solution of the imino di-ferric succinate into the monosultap dichloroethane solution in the step (4), wherein the concentration of the imino di-ferric succinate is 110 mg/L.
The purification process of the monosultap in the step (1) comprises the following steps:
1) dissolving monosultap in dichloroethane to obtain monosultap stock solution;
2) dispersing activated carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare activated carbon slurry;
3) wrapping activated carbon slurry on the surface of vermiculite, coupling and drying, and heating to 300 ℃ by using a muffle furnace to prepare the vermiculite adsorbent;
4) putting the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering to obtain the monosultap dichloroethane solution.
The mass of the activated carbon powder is 0.5 percent of the mass of the monosultap, the mass of the KH550 is 3 percent of the mass of the activated carbon powder, and the dosage of the vermiculite is 10 percent of the mass of the monosultap.
Example 3
A novel cyanidation process for synthesizing cartap comprises the following specific steps:
(1) dissolving monosultap in dichloroethane, adding adsorbent to remove impurities, and making into monosultap dichloroethane solution;
(2) adding alkali into water to adjust the pH value to 8, and then dissolving sodium cyanide with the molar weight 1.95 times that of monosultap in the water to prepare an alkaline solution of the sodium cyanide;
(3) mixing imino disuccinic acid and ferrous salt according to the molar ratio of 1:2, and adjusting the pH value to 7.1 to prepare an imino disuccinic acid diiron solution;
(4) mixing the imino di-succinic acid di-iron solution with the monosultap dichloroethane solution, stirring and mixing uniformly, cooling to 8 ℃,
(5) then dropwise adding an alkaline solution of sodium cyanide, keeping the temperature at 10 ℃ in the reaction process, keeping the temperature for reaction for 2 hours after dropwise adding, and standing for layering after the reaction is finished;
(6) separating the upper water phase to obtain cyanide-containing wastewater; the lower organic phase of thiocyanide is obtained.
The concentration of the monosultap dissolved in the dichloroethane in the step (1) is 4.91 g/L.
The ferrous salt in the step (3) is FeCl2。
And (4) mixing a solution of the imino di-ferric succinate into the monosultap dichloroethane solution in the step (4), wherein the concentration of the imino di-ferric succinate is 120 mg/L.
The purification process of the monosultap in the step (1) comprises the following steps:
1) dissolving monosultap in dichloroethane to obtain monosultap stock solution;
2) dispersing activated carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare activated carbon slurry;
3) wrapping activated carbon slurry on the surface of vermiculite, coupling and drying, and heating to 300 ℃ by using a muffle furnace to prepare the vermiculite adsorbent;
4) putting the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering to obtain the monosultap dichloroethane solution.
The mass of the activated carbon powder is 1 percent of that of the monosultap, the mass of the KH550 is 5 percent of that of the activated carbon powder, and the dosage of the vermiculite is 5 percent of that of the monosultap.
Comparative example 1
The cyanidation process of synthesizing cartap is the same as that in example 2, and has no adsorbent added to eliminate impurity from monosultap and sodium cyanide in the molar amount of 2.05 times that of monosultap.
Comparative example 2
A cyanidation process for synthesizing cartap, wherein the cyanidation process is not added with iminodisuccinic acid diiron, and specifically comprises the steps of regulating the pH value of a sodium cyanide solution to 10, cooling a monosultap dichloroethane solution to 0 ℃, controlling the reaction temperature to be 5 ℃ when the sodium cyanide solution is dripped, and the rest is the same as in example 2.
Comparative example 3
A cyanidation process for the synthesis of cartap, with no added diiron iminodisuccinate, as in example 2.
Detection and analysis:
the examples and comparative examples were conducted in pilot scale controlled laboratory safety closed conditions:
taking the monosultap dichloroethane solution prepared in the step (1), removing the solvent, and detecting the purity of the monosultap according to GB/T28128-2011 'monosultap raw drug'; washing the adsorbent with water, and detecting the adsorption ratio of the adsorbent to the monosultap;
the adsorption ratio (%) of the adsorbent is 100% of the mass of monosultap adsorbed by the adsorbent/total mass of monosultap
Detecting the purity of the thiocyanide prepared by the cyanidation reaction by the same method, and calculating the conversion rate of the monosultap;
monitoring on the liquid surface of the cyanidation reaction by a hydrocyanic acid detector with a detection limit of 0.1ppm, recording whether hydrocyanic acid escapes in the cyanidation reaction process, and detecting the content of cyanide ions in the cyanide-containing wastewater.
The invention can effectively reduce the impurity content of monosultap through the adsorbent, improve the monosultap conversion rate and the purity of thiocyanide, reduce the using amount of sodium cyanide, and reduce the concentration of cyanide ions in cyanide-containing wastewater; the improvement of the purity of the thiocyanide is beneficial to the improvement of the conversion rate of the subsequent hydrolysis reaction, compared with the cartap total yield of 82-84% in the common process, the cartap total yield of the process can reach 90-92%, and the purity of the cartap is also improved;
the invention can reduce the adsorption capacity to monosultap by cross-linking the vermiculite and the activated carbon powder, and the adsorbent has a carrier and is easy to filter and separate;
according to the invention, cyanide ions in a cyanidation reaction system can be effectively stabilized through the diiron iminodisuccinate, so that hydrocyanic acid gas cannot be formed to escape, the temperature of the reaction system can be increased, and the energy consumption of cyanidation reaction refrigeration is reduced; and the imino di-ferrous succinate is added, so that the treatment efficiency and safety of the cyanide-containing wastewater can be improved.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. A novel cyaniding process for synthesizing cartap is characterized in that: the cyanidation process is specifically as follows:
(1) dissolving monosultap in dichloroethane, adding adsorbent to remove impurities, and making into monosultap dichloroethane solution;
(2) adding alkali into water to adjust the pH value to 8-9, and then dissolving sodium cyanide with the molar weight of 1.95-1.98 times that of monosultap in the water to prepare an alkaline solution of the sodium cyanide;
(3) mixing imino disuccinic acid and ferrous salt according to the molar ratio of 1:2, and adjusting the pH value to 7-8 to prepare an imino disuccinic acid diiron solution;
(4) mixing the imino di-succinic acid di-iron solution with the monosultap dichloroethane solution, stirring and mixing uniformly, cooling to 5-8 ℃,
(5) then dropwise adding an alkaline solution of sodium cyanide, keeping the temperature less than or equal to 10 ℃ in the reaction process, preserving heat for reaction for 2 hours after dropwise adding is finished, and standing for layering after the reaction is finished;
(6) separating the upper water phase to obtain cyanide-containing wastewater; the lower organic phase of thiocyanide is obtained.
2. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: the concentration of the monosultap dissolved in the dichloroethane in the step (1) is 4.91 g/L-4.95 g/L.
3. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: the ferrous salt in the step (3) is FeCl2Or FeSO4。
4. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: and (4) mixing the solution of the iminodisuccinic acid with the solution of the iminodisuccinic acid diiron to obtain the concentration of the iminodisuccinic acid diiron of 100 mg/L-120 mg/L.
5. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: the adsorbent in the step (1) is activated carbon with the mass of 0.5-1% of the monosultap, and the activated carbon is filtered after adsorption is finished to prepare the monosultap dichloroethane solution.
6. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: the process for removing impurities by adding the adsorbent in the step (1) comprises the following steps:
1) dissolving monosultap in dichloroethane to obtain monosultap stock solution;
2) dispersing activated carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare activated carbon slurry;
3) wrapping activated carbon slurry on the surface of vermiculite, coupling and drying, and heating to 300 ℃ by using a muffle furnace to prepare the vermiculite adsorbent;
4) putting the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering to obtain the monosultap dichloroethane solution.
7. A new cyanidation process for the synthesis of cartap according to claim 6, characterized in that: the mass of the activated carbon powder is 0.5-1 percent of that of the monosultap, the mass of the KH550 is 3-5 percent of that of the activated carbon powder, and the dosage of the vermiculite is 5-10 percent of that of the monosultap.
8. A new cyanidation process for the synthesis of cartap according to claim 1, characterized in that: after the adsorption of the adsorbent is finished, filtering, washing with water and recrystallizing to recover the adsorbed monosultap.
9. Cartap prepared by a cyanidation process using the novel synthetic cartap of any one of claims 1 to 8 and then by hydrolysis.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1089573A (en) * | 1977-03-19 | 1980-11-11 | Toshio Iwase | Method for treating waste water containing cyanide ion |
| WO2001030473A1 (en) * | 1999-10-27 | 2001-05-03 | Board Of Regents Of The University And Community College System Of Nevada | Cyanide detoxification process |
| CN101302179A (en) * | 2008-06-23 | 2008-11-12 | 江苏天容集团股份有限公司 | Solvent process for synthesizing cartap |
| CN105348160A (en) * | 2014-08-21 | 2016-02-24 | 天津市汇源化学品有限公司 | New green and environmental-protection technology for production of cartap |
| US20160302417A1 (en) * | 2015-04-17 | 2016-10-20 | Dow Agrosciences Llc | Molecules Having Pesticidal Utility, and Intermediates, Compositions, and Processes, Related Thereto |
| CN110981048A (en) * | 2019-12-18 | 2020-04-10 | 安徽华星化工有限公司 | Method for treating cyanide-containing wastewater in cartap synthesis process |
-
2021
- 2021-03-22 CN CN202110302057.7A patent/CN113200897B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1089573A (en) * | 1977-03-19 | 1980-11-11 | Toshio Iwase | Method for treating waste water containing cyanide ion |
| WO2001030473A1 (en) * | 1999-10-27 | 2001-05-03 | Board Of Regents Of The University And Community College System Of Nevada | Cyanide detoxification process |
| CN101302179A (en) * | 2008-06-23 | 2008-11-12 | 江苏天容集团股份有限公司 | Solvent process for synthesizing cartap |
| CN105348160A (en) * | 2014-08-21 | 2016-02-24 | 天津市汇源化学品有限公司 | New green and environmental-protection technology for production of cartap |
| US20160302417A1 (en) * | 2015-04-17 | 2016-10-20 | Dow Agrosciences Llc | Molecules Having Pesticidal Utility, and Intermediates, Compositions, and Processes, Related Thereto |
| CN110981048A (en) * | 2019-12-18 | 2020-04-10 | 安徽华星化工有限公司 | Method for treating cyanide-containing wastewater in cartap synthesis process |
Non-Patent Citations (1)
| Title |
|---|
| 张静韵: "《电镀工艺学》", 科学普及出版社, pages: 120 - 121 * |
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