CN113200897B - Novel cyanidation process for synthesizing cartap - Google Patents
Novel cyanidation process for synthesizing cartap Download PDFInfo
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- CN113200897B CN113200897B CN202110302057.7A CN202110302057A CN113200897B CN 113200897 B CN113200897 B CN 113200897B CN 202110302057 A CN202110302057 A CN 202110302057A CN 113200897 B CN113200897 B CN 113200897B
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- monosultap
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- dichloroethane
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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 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 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 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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 32
- 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 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 25
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 25
- 239000010455 vermiculite Substances 0.000 claims abstract description 25
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940080260 iminodisuccinate Drugs 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 50
- 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 23
- 238000002156 mixing Methods 0.000 claims description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000000749 insecticidal effect Effects 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 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
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 14
- 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
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 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
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical compound CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 238000007333 cyanation reaction Methods 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
- 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
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 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
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
Abstract
The invention discloses a novel cyanidation process for synthesizing cartap, which reduces the content of monosultap impurity through an adsorbent, improves the conversion rate of monosultap and reduces the dosage of sodium cyanide; through cross-linking of vermiculite and activated carbon powder, the vermiculite is burned to form a great proportion of deformation, the selective adsorption performance is improved, and the adsorption quantity of monosultap is reduced; cyanide ions in the cyanidation reaction system can be effectively stabilized through the iminodisuccinate, so that hydrocyanic acid gas cannot be formed to overflow, the control condition of the existing process can be reduced, and the energy consumption of cyanidation refrigeration is reduced; meanwhile, the cyanide ion content of the cyanide-containing wastewater is obviously reduced, and the treatment efficiency and the safety of the cyanide-containing wastewater are obviously improved.
Description
Technical Field
The invention relates to a synthesis process of cartap, in particular to a novel cyanidation process for synthesizing cartap.
Background
Cartap, commonly known as Cartap hydrochloride, the name bardan, is also known chemically as 1, 3-bis (carbamoylthio) -2-dimethylaminopropane hydrochloride. Cartap is a nereistoxin pesticide, has the characteristics of broad spectrum, high efficiency, low toxicity and the like, and has been widely used for preventing and controlling pests of various crops such as rice, vegetables, fruit trees and the like. In the times of stronger environmental protection concept and health concept, the low toxicity characteristic of cartap makes cartap more and more important.
In the prior art, the cartap is mainly synthesized by taking the cartap as a raw material, and is prepared through cyanation 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, the reaction principle is as follows:
wherein, the theoretical molar ratio of monosultap to sodium cyanide is 1:2.
However, in general, to ensure that the monosultap reaction is complete, the amount of sodium cyanide used is in excess, typically 2.05 to 2.1 times the molar amount of monosultap. However, the process can lead to excessive sodium cyanide, waste water containing sodium cyanide is formed after the reaction is completed, and sodium cyanide and hydrocyanic acid generated after acidification of sodium cyanide are extremely toxic substances.
Meanwhile, the general purity of the insecticidal composition is about 95%, the conversion rate of the cyanidation reaction is affected by the residual impurities, so that the utilization rate of the insecticidal composition is low, the sodium cyanide is consumed excessively, the cyanide concentration in the wastewater containing the sodium cyanide reaches about 5000mg/L, the waste of raw materials is caused, and the high-concentration cyanide wastewater is a great dangerous source.
Therefore, a novel cyanidation process for synthesizing cartap needs to be developed, the consumption of raw materials is reduced, and cyanide ions in an aqueous phase are stabilized.
Disclosure of Invention
The invention develops a novel cyanidation process for synthesizing cartap, which can effectively reduce the consumption of raw materials and stabilize cyanide ions in an aqueous phase.
A novel cyanidation process for synthesizing cartap comprises the following steps:
(1) Dissolving monosultap in dichloroethane, adding adsorbent to remove impurity, and making into monosultap dichloroethane solution;
(2) Adding alkali into water to regulate the pH value to 8-9, and dissolving sodium cyanide with 1.95-1.98 times of insecticidal single molar weight into water to prepare sodium cyanide alkaline solution;
(3) Mixing iminodisuccinic acid and ferrous salt according to a molar ratio of 1:2, and regulating the pH value to 7-8 to prepare an iminodisuccinic acid ferric solution;
(4) Mixing the iminodisuccinic acid ferric solution into monosultap dichloroethane solution, stirring and uniformly mixing, cooling to 5-8 ℃,
(5) Then dropwise adding sodium cyanide alkaline solution, keeping the temperature at less than or equal to 10 ℃ in the reaction process, preserving heat for 2 hours after the dropwise adding is finished, and standing for layering after the reaction is finished;
(6) Separating an upper water phase which is cyanide-containing wastewater; the lower thiocyanide organic phase is obtained.
The organic phase of thiocyanide prepared by the process is added with water and methanol, then hydrogen chloride gas is introduced for hydrolysis reaction, cartap solution can be prepared, and cartap can be prepared by removing solvent and crystallizing.
Further, the concentration of the monosultap dissolved in dichloroethane in the step (1) is 4.91g/L to 4.95g/L.
Further, the ferrous salt in the step (3) is FeCl 2 Or FeSO 4 。
Further, after the iminodisuccinic acid ferric solution is mixed into the monosultap dichloroethane solution in the step (4), the concentration of the iminodisuccinic acid ferric is 100mg/L to 120mg/L.
Further, the purification process of the monosultap in the step (1) is to add activated carbon accounting for 0.5-1% of the mass of the monosultap, and filter out the activated carbon after the adsorption is finished to prepare the monosultap dichloroethane solution.
Further, the purification process of the monosultap in the step (1) is as follows:
1) The monosultap is dissolved in dichloroethane to obtain monosultap stock solution;
2) Dispersing active carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare active carbon slurry;
3) Coating active carbon slurry on the surface of vermiculite, and heating to 300 ℃ by a muffle furnace after coupling and drying to prepare the vermiculite adsorbent;
4) And (3) adding the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering out the vermiculite adsorbent to obtain the monosultap dichloroethane solution.
Further, the active carbon powder accounts for 0.5 to 1 percent of the mass of the monosultap, KH550 accounts for 3 to 5 percent of the mass of the active carbon powder, and the vermiculite accounts for 5 to 10 percent of the mass of the monosultap.
Further, the filtered adsorbent can be washed with water and recrystallized to recover the adsorbed monosultap.
The invention has the advantages that:
1. according to the invention, the monosultap is pulped, wherein impurity sodium salt and part of organic impurities form a suspension body, the content of the monosultap impurity can be effectively reduced through the adsorbent, the monosultap conversion rate is improved, and the sodium cyanide consumption is reduced;
2. according to the invention, vermiculite and activated carbon powder are crosslinked and then burnt to form a great proportion of deformation, so that the selective adsorption performance is improved, and the adsorption quantity of monosultap is reduced; the solubility of the monosultap in the dichloroethane is low, namely about 0.39g/100mL of dichloroethane, so that the amount of the adsorbent is very small, and compared with the activated carbon, the adsorbent obtained by crosslinking vermiculite and activated carbon powder is very easy to filter and separate;
3. according to the invention, cyanide ions in a cyanide reaction system can be effectively stabilized through the diiodo-ferrous iminodisuccinate, so that hydrocyanic acid gas cannot be formed to escape; the prior art aims at preventing hydrocyanic acid gas from overflowing, adjusting the pH value of the sodium cyanide solution to about 10, and controlling the reaction temperature to be between 0 and 5 ℃, but the invention can reduce the pH value of the sodium cyanide solution, and improve the reaction temperature to 10 ℃, thereby reducing the energy consumption of cyanidation refrigeration;
4. according to the invention, through adding the iminodisuccinate, the treatment efficiency and the safety of cyanide-containing wastewater can be improved.
Detailed Description
Example 1
A novel cyanidation process for synthesizing cartap comprises the following steps:
(1) Dissolving monosultap in dichloroethane, adding adsorbent to remove impurity, and making into monosultap dichloroethane solution;
(2) Adding alkali into water to adjust the pH value to 9, and then dissolving sodium cyanide with 1.98 times of the single molar weight of the insecticide into the water to prepare an alkaline sodium cyanide solution;
(3) Mixing iminodisuccinic acid and ferrous salt according to a molar ratio of 1:2, and regulating the pH value to 8.0 to prepare an iminodisuccinic acid ferric solution;
(4) Mixing the iminodisuccinic acid ferric solution into monosultap dichloroethane solution, stirring and uniformly mixing, cooling to 5 ℃,
(5) Then dropwise adding sodium cyanide alkaline solution, keeping the temperature at 8 ℃ in the reaction process, preserving heat for 2 hours after the dropwise adding is finished, and standing for layering after the reaction is finished;
(6) Separating an upper water phase which is cyanide-containing wastewater; the lower thiocyanide organic phase is obtained.
The concentration of the monosultap dissolved in dichloroethane in the step (1) is 4.95g/L.
The ferrous salt in the step (3) is FeSO 4 。
And (4) mixing the monosultap dichloroethane solution with an iminodisuccinate ferric solution, wherein the concentration of the iminodisuccinate ferric solution is 100mg/L.
The purification process of the monosultap in the step (1) is to add activated carbon accounting for 0.8 percent of the mass of the monosultap, and filter out the activated carbon after the adsorption is finished to prepare the monosultap dichloroethane solution.
Example 2
A novel cyanidation process for synthesizing cartap comprises the following steps:
(1) Dissolving monosultap in dichloroethane, adding adsorbent to remove impurity, 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 1.96 times of insecticidal single molar weight into the water to prepare an alkaline sodium cyanide solution;
(3) Mixing iminodisuccinic acid and ferrous salt according to a molar ratio of 1:2, and regulating the pH value to 7.7 to prepare an iminodisuccinic acid ferric solution;
(4) Mixing the iminodisuccinic acid ferric solution into monosultap dichloroethane solution, stirring and uniformly mixing, cooling to 7 ℃,
(5) Then dropwise adding sodium cyanide alkaline solution, keeping the temperature at 10 ℃ in the reaction process, preserving heat for 2 hours after the dropwise adding is finished, and standing for layering after the reaction is finished;
(6) Separating an upper water phase which is cyanide-containing wastewater; the lower thiocyanide organic phase is obtained.
The concentration of the monosultap dissolved in dichloroethane in the step (1) is 4.92g/L.
The ferrous salt in the step (3) is FeCl 2 。
And (4) mixing the monosultap dichloroethane solution with an iminodisuccinate ferric solution, wherein the concentration of the iminodisuccinate ferric solution is 110mg/L.
The purification process of the monosultap in the step (1) comprises the following steps:
1) The monosultap is dissolved in dichloroethane to obtain monosultap stock solution;
2) Dispersing active carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare active carbon slurry;
3) Coating active carbon slurry on the surface of vermiculite, and heating to 300 ℃ by a muffle furnace after coupling and drying to prepare the vermiculite adsorbent;
4) And (3) adding the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering out the vermiculite adsorbent to obtain the monosultap dichloroethane solution.
The mass of the active carbon powder is 0.5% of that of the monosultap, the mass of the KH550 is 3% of that of the active carbon powder, and the using amount of the vermiculite is 10% of that of the monosultap.
Example 3
A novel cyanidation process for synthesizing cartap comprises the following steps:
(1) Dissolving monosultap in dichloroethane, adding adsorbent to remove impurity, and making into monosultap dichloroethane solution;
(2) Adding alkali into water to adjust the pH value to 8, and then dissolving sodium cyanide with 1.95 times of the single molar weight of the insecticide into the water to prepare an alkaline sodium cyanide solution;
(3) Mixing iminodisuccinic acid and ferrous salt according to a molar ratio of 1:2, and regulating the pH value to 7.1 to prepare an iminodisuccinic acid ferric solution;
(4) Mixing the iminodisuccinic acid ferric solution into monosultap dichloroethane solution, stirring and uniformly mixing, cooling to 8 ℃,
(5) Then dropwise adding sodium cyanide alkaline solution, keeping the temperature at 10 ℃ in the reaction process, preserving heat for 2 hours after the dropwise adding is finished, and standing for layering after the reaction is finished;
(6) Separating an upper water phase which is cyanide-containing wastewater; the lower thiocyanide organic phase is obtained.
The concentration of the monosultap dissolved in dichloroethane in the step (1) is 4.91g/L.
The ferrous salt in the step (3) is FeCl 2 。
And (4) mixing the monosultap dichloroethane solution with an iminodisuccinate ferric solution, wherein the concentration of the iminodisuccinate ferric solution is 120mg/L.
The purification process of the monosultap in the step (1) comprises the following steps:
1) The monosultap is dissolved in dichloroethane to obtain monosultap stock solution;
2) Dispersing active carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare active carbon slurry;
3) Coating active carbon slurry on the surface of vermiculite, and heating to 300 ℃ by a muffle furnace after coupling and drying to prepare the vermiculite adsorbent;
4) And (3) adding the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering out the vermiculite adsorbent to obtain the monosultap dichloroethane solution.
The mass of the active carbon powder is 1% of that of the monosultap, the mass of the KH550 is 5% of that of the active carbon powder, and the using amount of the vermiculite is 5% of that of the monosultap.
Comparative example 1
A cyanidation process for synthesizing cartap, which is free of an adsorbent to remove impurities in monosultap, uses sodium cyanide with a molar quantity which is 2.05 times that of the monosultap, and the rest is the same as in example 2.
Comparative example 2
A cyanidation process for synthesizing cartap, which is characterized in that iminodisuccinate is not added, the cyanidation process is specifically that a sodium cyanide solution is used for regulating the pH value to 10, a monosultap dichloroethane solution is cooled to 0 ℃, the reaction temperature is controlled to 5 ℃ when the sodium cyanide solution is added dropwise, and the rest is the same as that in example 2.
Comparative example 3
A cyanidation process for synthesizing cartap, which is free of added iminodisuccinate, is the same as in example 2.
Detection and analysis:
each example and comparative example were subjected to a pilot run under controlled laboratory safety containment 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 original drug"; washing the adsorbent with water, and detecting the adsorption ratio of the adsorbent to monosultap;
adsorbent adsorption ratio (%) =adsorbent adsorbed monosultap mass/monosultap total mass 100%
Detecting the purity of the thiocyanide prepared by the cyanidation reaction by the same method, and calculating the conversion rate of monosultap;
the hydrocyanic acid detector with the detection limit of 0.1ppm is used for monitoring the surface of the cyanidation liquid, recording whether hydrocyanic acid escapes in the cyanidation process, and detecting the cyanide ion content in cyanide-containing wastewater.
The invention can effectively reduce the impurity content of the monosultap through the adsorbent, improve the conversion rate of the monosultap and the purity of the thiocyanide, reduce the dosage of sodium cyanide and reduce the concentration of cyanide ions in cyanide-containing wastewater; compared with the total yield of cartap 82-84% in the common process, the total yield of cartap can reach 90-92%, and the purity of cartap is also improved;
the invention can reduce the adsorption quantity of the monosultap by cross-linking vermiculite and activated carbon powder, and the adsorbent is provided with a carrier, thus being extremely easy to filter and separate;
according to the invention, cyanide ions in the cyanidation reaction system can be effectively stabilized through the 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 refrigeration is reduced; and the added iminodisuccinate can improve the treatment efficiency and the safety of cyanide-containing wastewater.
Finally: the foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A novel cyanidation process for synthesizing cartap is characterized in that: the cyanidation process comprises the following steps:
(1) The monosultap is dissolved in dichloroethane, and the adsorbent is added to remove impurities to prepare monosultap dichloroethane solution, which has the following process:
1) The monosultap is dissolved in dichloroethane to obtain monosultap stock solution;
2) Dispersing active carbon powder in water to prepare suspension, adding a small amount of hydrogen peroxide, activating, adding KH550, and completely dispersing to prepare active carbon slurry;
3) Coating active carbon slurry on the surface of vermiculite, and heating to 300 ℃ by a muffle furnace after coupling and drying to prepare the vermiculite adsorbent;
4) Adding the vermiculite adsorbent into the monosultap stock solution, stirring, and filtering out the vermiculite adsorbent to obtain monosultap dichloroethane solution;
wherein, the active carbon powder is 0.5 to 1 percent of the mass of the monosultap, KH550 is 3 to 5 percent of the mass of the active carbon powder, and the vermiculite dosage is 5 to 10 percent of the mass of the monosultap;
(2) Adding alkali into water to regulate the pH value to 8-9, and dissolving sodium cyanide with 1.95-1.98 times of insecticidal single molar weight into water to prepare sodium cyanide alkaline solution;
(3) Mixing iminodisuccinic acid and ferrous salt according to a molar ratio of 1:2, and regulating the pH value to 7-8 to prepare an iminodisuccinic acid ferric solution;
(4) Mixing the iminodisuccinic acid ferric solution into monosultap dichloroethane solution, stirring and uniformly mixing, cooling to 5-8 ℃,
(5) Then dropwise adding sodium cyanide alkaline solution, keeping the temperature at less than or equal to 10 ℃ in the reaction process, preserving heat for 2 hours after the dropwise adding is finished, and standing for layering after the reaction is finished;
(6) Separating an upper water phase which is cyanide-containing wastewater; the lower thiocyanide organic phase is obtained.
2. A novel cyanidation process for the synthesis of cartap as claimed in claim 1, wherein: the concentration of the monosultap dissolved in dichloroethane in the step (1) is 4.91g/L to 4.95g/L.
3. A novel cyanidation process for the synthesis of cartap as claimed in claim 1, wherein: the ferrous salt in the step (3) is FeCl 2 Or FeSO 4 。
4. A novel cyanidation process for the synthesis of cartap as claimed in claim 1, wherein: and (4) mixing the monosultap dichloroethane solution with an iminodisuccinate ferric solution, wherein the concentration of the iminodisuccinate ferric solution is 100-120 mg/L.
5. A novel cyanidation process for the synthesis of cartap as claimed in claim 1, wherein: after the adsorption of the adsorbent is finished, the adsorbent can be filtered out, washed with water and recrystallized to recover the adsorbed monosultap.
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| CN202110302057.7A CN113200897B (en) | 2021-03-22 | 2021-03-22 | Novel cyanidation process for synthesizing cartap |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110302057.7A CN113200897B (en) | 2021-03-22 | 2021-03-22 | Novel cyanidation process for synthesizing cartap |
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| Publication Number | Publication Date |
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| 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 |
| 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 |
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| CA2980345C (en) * | 2015-04-17 | 2024-03-05 | Dow Agrosciences Llc | Cyclopropyl amide derivatives having pesticidal utility, and intermediates, compositions, and processes, related thereto |
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| 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 |
| 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 |
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