CN117488318A - Comprehensive treatment method for rubber accelerator byproduct sulfonate - Google Patents
Comprehensive treatment method for rubber accelerator byproduct sulfonate Download PDFInfo
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- CN117488318A CN117488318A CN202311789126.7A CN202311789126A CN117488318A CN 117488318 A CN117488318 A CN 117488318A CN 202311789126 A CN202311789126 A CN 202311789126A CN 117488318 A CN117488318 A CN 117488318A
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000006227 byproduct Substances 0.000 title claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000012528 membrane Substances 0.000 claims abstract description 57
- 239000007864 aqueous solution Substances 0.000 claims abstract description 43
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000005185 salting out Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000003011 anion exchange membrane Substances 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 6
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 210000005056 cell body Anatomy 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the field of wastewater treatment, and particularly relates to a comprehensive treatment method of rubber accelerator byproduct sulfonate, which comprises the following steps: 1) Lowering Wen Yanxi the waste water discharged from the accelerator production unit; 2) Adding water into the solid salt to prepare sulfonate aqueous solution; 3) The sulfonate aqueous solution enters an electrolytic tank for electrolysis. According to the technical scheme, firstly, through a simple physical salting-out process, supersaturated sodium chloride salt water is used for precipitating sodium sulfonate, the purity of the sodium sulfonate is higher than 94%, then, 8% aqueous solution of sulfonic acid and 8% aqueous solution of sodium hydroxide are obtained through double-stage membrane electrolysis, and the alkali liquor with low solubility can be applied to various accelerator production processes.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a comprehensive treatment method of rubber accelerator byproduct sulfonate.
Background
The rubber accelerator comprises TBBS, CBS, DCBS, namely raw material MBT (2-mercaptobenzothiazole) is used in the production process, the MBT yield of TBBS in the current mainstream production process is 92%, the CBS yield is 88%, the DCBS yield is 80%, a large amount of MBT generates byproduct sulfonate in the oxidation process, the general scheme of the accelerator manufacturer for the sulfonate is that normal salt is generated by incineration, the utilization rate of the scheme for the byproduct is limited, and the national industrial policy of increasing a large amount of carbon emission and reducing carbon in the incineration process is not consistent. So the effective use of the organic salt becomes a problem to be solved by the accelerator enterprises.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a comprehensive treatment method for rubber accelerator byproduct sulfonate.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a comprehensive treatment method of rubber accelerator byproduct sulfonate comprises the following steps: 1) Cooling the residual wastewater discharged from the accelerator production unit to 25-40 ℃ for salting out;
2) Dissolving solid salt separated out by salt in water to prepare sulfonate aqueous solution with the mass concentration of 5-10%;
3) And (3) the sulfonate aqueous solution enters an electrolytic tank for electrolysis to obtain a sulfonate aqueous solution and a sodium hydroxide aqueous solution.
Preferably, in the step 1), the temperature is reduced to 30 ℃ for salting out.
The salting-out process in the step 1) is to add supersaturated sodium chloride solution, so that the sodium chloride content in the wastewater is ensured to be more than 24%.
The aqueous solution of sulfonate with the mass concentration of 8% is prepared in the step 2).
The electrolytic tank in the step 3) is a two-stage membrane electrolytic tank;
the two-stage membrane electrolytic cell comprises an electrolytic cell body, an anode and a cathode which are arranged at two sides of the electrolytic cell body, and a two-stage membrane unit which is arranged between the anode and the cathode; the two-stage membrane unit comprises a first two-stage membrane, an anion exchange membrane, a cation exchange membrane and a second two-stage membrane which are sequentially arranged from an anode to a cathode;
an anode chamber is formed between the anode and the first two-stage membrane; an acid chamber is formed between the first two-stage membrane and the anion exchange membrane, and a salt chamber is formed between the anion exchange membrane and the cation exchange membrane; an alkali chamber is formed between the cation exchange membrane and the second double-stage membrane; the second dual-stage membrane forms a cathode chamber with the cathode.
The waste water discharged from the accelerator production unit in the step 1) is derived from waste water generated in the preparation process of the accelerator TBBS, the accelerator CBS and the accelerator DCBS.
Preferably, the waste water discharged from the accelerator production unit in step 1) is derived from waste water generated during the preparation of the accelerator CBS;
the preparation process of the accelerator CBS comprises the following steps:
(a) Preparing an M-Na salt solution: mixing accelerator MBT with NaOH aqueous solution with mass concentration of 20% -35% to prepare M-Na salt solution;
wherein the mass ratio of the accelerator MBT to the NaOH aqueous solution is 1 (0.5-1.5), the mixing time is 0-2 h, and the mixing temperature is 40-60 ℃;
preparing an acid solution of cyclohexylamine: mixing cyclohexylamine with an acid solution with the mass concentration of 20-30% at 40-45 ℃ under the stirring condition to obtain an acid solution of cyclohexylamine; wherein, the mol ratio of the cyclohexane to the solute in the acid solution is 1 (0.3-1), and the mass ratio of the cyclohexane to the water is 1 (0.5-1);
(b) Introducing an M-Na salt solution, an acid solution of cyclohexylamine, a solvent and an oxidant solution into a microchannel reactor to perform oxidation reaction at 20-50 ℃, wherein the reaction residence time is 0.5-10 s;
wherein, the feeding mass ratio of the M-Na salt solution to the acid solution of the cyclohexylamine is 1 (1-2.5), the feeding mass ratio of the M-Na salt solution to the solvent is 1 (1.5-3), and the feeding mass ratio of the M-Na salt solution to the oxidant solution is 1 (1.2-4);
(c) The materials after oxidation are decompressed and evaporated to recycle the solvent under the conditions of 40 ℃ to 80 ℃ and the vacuum degree of 10kPa to 50kPa, and the rest is waste water after the CBS crude product is obtained by filtration.
The acid solution is aqueous solution of hydrochloric acid, sulfuric acid or nitric acid; the solvent is one or a mixed solution of ethyl acetate and toluene; the oxidant is sodium hypochlorite.
The method also comprises the step 4) of evaporating the aqueous solution of sulfonic acid and/or the aqueous solution of sodium hydroxide to obtain pure product sulfonic acid and/or sodium hydroxide; the evaporated water is used to dissolve the solid salt in step 2).
Compared with the prior art, the invention has the beneficial effects that:
in the technical scheme of the application, firstly, through a simple physical salting-out process, the sulfonate is separated out by using supersaturated sodium chloride salt water, and the purity of the obtained sulfonate can be generally higher than 94%; then 8% aqueous solution of sulfonic acid and 8% aqueous solution of sodium hydroxide are obtained by double-stage membrane electrolysis, and the alkali liquor with low solubility can be applied to various accelerator production processes;
as the preferential selection, biochemical effluent obtained by evaporating a sulfonic acid aqueous solution and a sodium hydroxide aqueous solution is used for dissolving solid salt, so that the biochemical effluent is effectively recycled, and the water system is ensured to be used mechanically without generating extra water.
The technical scheme of the application is that the byproduct sulfonic acid is applied to various industries including catalyst industry and the like. Meanwhile, the method does not adopt the traditional incineration process, has obvious control advantage on national carbon emission indexes, and is a low-carbon emission process.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following examples, wherein the concentrations are mass concentrations unless otherwise specified.
Example 1A method for comprehensive treatment of rubber accelerator by-product sulfonate, comprising the following steps:
1) Cooling the residual wastewater of the accelerator production unit to 25 ℃, 30 ℃ and 40 ℃ and adding sodium chloride for salting out, wherein the salting out process is to add supersaturated sodium chloride solution, so that the sodium chloride content in the wastewater is ensured to be more than 24%, and the result is shown in table 1;
TABLE 1
Temperature lowering (DEG C) | Purity of sodium salt of salted out sulfonic acid | Residual sulfonate in water |
25 | 96.0% | 5.6% |
30 | 95.4% | 3.2% |
40 | 94.3% | 4.3% |
Taking energy consumption and salting-out effect into consideration, carrying out the experiment of the step 2) by taking sodium sulfonate obtained at 30 ℃ as a preferred example;
the waste water discharged from the accelerator production unit in the embodiment of the application comes from waste water generated in the preparation process of the accelerator CBS, and as the accelerator TBBS, CBS, DCBS uses the raw material MBT (2-mercaptobenzothiazole) in the production process, byproduct sulfonate is generated in the oxidation process, the technical scheme of the application is suitable for waste water generated in the production process of the accelerator TBBS, CBS, DCBS, and is particularly suitable for a comprehensive treatment method of the sulfonate of the accelerator CBS;
the preparation process of the accelerator CBS is taken as an example for illustration in the application: the method specifically comprises the following steps:
(a) Preparing an M-Na salt solution: mixing accelerator MBT with NaOH aqueous solution with mass concentration of 30% (which can be adjusted to 20% and 35%) to prepare M-Na salt solution;
wherein, the mass ratio of the accelerator MBT to the NaOH aqueous solution is 1:1 (0.5 and 1.5 can be adjusted), the mixing time is 1h (0.5 h and 2h can be adjusted), and the mixing temperature is 40 ℃ (50 ℃ and 60 ℃);
preparing an acid solution of cyclohexylamine: mixing cyclohexylamine with 25% (which can be adjusted to 20% and 30%) hydrochloric acid aqueous solution under stirring at 40deg.C (which can be adjusted to 45deg.C) to obtain cyclohexylamine acid solution;
wherein, the mol ratio of the cyclohexylamine to the solute in the acid solution is 1:0.5 (which can be adjusted to be 1:0.3 and 1:1), and the mass ratio of the cyclohexylamine to the water is 1:0.8 (which can be adjusted to be 1:0.5 and 1:1);
(b) Introducing an M-Na salt solution, an acid solution of cyclohexylamine, ethyl acetate (which can be partially or completely replaced by toluene) serving as a solvent and a sodium hypochlorite solution serving as an oxidant into a microchannel reactor to perform oxidation reaction at 35 ℃ (which can be adjusted to 20 ℃ and 50 ℃), wherein the residence time of the reaction is 2s (which can be adjusted to 0.5s and 10 s);
wherein, the feeding mass ratio of the M-Na salt solution and the acid solution of the cyclohexylamine is 1:2 (which can be adjusted to be 1:1 and 1:2.5), the feeding mass ratio of the M-Na salt solution and the solvent is 1:2 (which can be adjusted to be 1:1.5 and 1:3), and the feeding mass ratio of the M-Na salt solution and the oxidant solution is 1:2 (which can be adjusted to be 1:1.1 and 1:4);
(c) Evaporating the material after oxidation reaction under reduced pressure at 60 ℃ (which can be adjusted to 40 ℃ and 80 ℃) and vacuum degree of 20kPa (which can be adjusted to 10kPa and 50 kPa) to recover the solvent, and filtering to obtain a CBS crude product, wherein the rest is the needed wastewater;
(2) Salting out sodium chloride solid to obtain sodium sulfonate solid 95.4%, dissolving the sodium sulfonate solid by pure water (or water evaporated and recovered in the step 4), dissolving the sodium sulfonate solid into 5%, 8% and 10% of sulfonate water according to the feeding requirement of a double-stage membrane electrolytic cell, and taking 8% of sulfonate water solution as a preferred embodiment for the following description;
(3) The sulfonate aqueous solution enters an electrolytic tank for electrolysis to obtain a sulfonate aqueous solution and a sodium hydroxide aqueous solution;
the electrolytic tank in the embodiment is a double-stage membrane electrolytic tank commonly used in the prior art; the two-stage membrane electrolyzer generally comprises an electrolyzer body, an anode and a cathode which are arranged at two sides of the electrolyzer body, and a two-stage membrane unit which is arranged between the anode and the cathode; the two-stage membrane unit comprises a first two-stage membrane, an anion exchange membrane, a cation exchange membrane and a second two-stage membrane which are sequentially arranged from an anode to a cathode;
an anode chamber is formed between the anode and the first two-stage membrane; an acid chamber is formed between the first two-stage membrane and the anion exchange membrane, and a salt chamber is formed between the anion exchange membrane and the cation exchange membrane; an alkali chamber is formed between the cation exchange membrane and the second double-stage membrane; the second dual-stage membrane and the cathode form a cathode chamber;
the specific implementation process is as follows: and 2) the sulfonate aqueous solution obtained in the step 2) enters a salt chamber, sulfonate migrates to an acid chamber through an anion exchange membrane under the action of a direct current electric field, and when the sulfonate meets the positive membrane surface of the first bipolar membrane, the sulfonate cannot migrate continuously because the positive membrane surface is negatively charged, and the sulfonate stays in the acid chamber and combines with hydrogen ions decomposed from the positive membrane surface of the first bipolar membrane to generate sulfonic acid.
Under the action of a direct current electric field, sodium ions migrate to the alkaline chamber through the cation exchange membrane and encounter the negative membrane surface of the second bipolar membrane, and sodium ions cannot migrate continuously and remain in the alkaline chamber because of positive electricity of the positive membrane surface and are combined with hydroxide ions continuously decomposed from the negative membrane surface of the second bipolar membrane under the action of the direct current electric field to generate sodium hydroxide.
Thus, the sulfonate of the salt chamber continuously enters the acid chamber, so that the acid liquid concentration is continuously improved. Sodium ions continuously enter an alkali chamber to receive hydroxide ions decomposed by the bipolar membrane, and the concentration of the alkali solution is continuously increased. The final sodium sulfonate is converted to sulfonic acid and sodium hydroxide solution by bipolar membrane electrodialysis.
Double-stage membrane electrolysis is carried out to obtain 8% aqueous solution of sulfonic acid and 8% aqueous solution of sodium hydroxide, which are respectively used as downstream application, and low-solubility alkali liquor can be applied to various accelerator production processes;
4) The aqueous solution of sulfonic acid and/or aqueous solution of sodium hydroxide can also be evaporated to obtain pure product of sulfonic acid and/or sodium hydroxide. The evaporated wastewater enters a biochemical link to obtain purified water with COD <150, and the purified water can be circularly applied to the dissolution process of the sulfonate in the step 2).
In summary, it can be seen that in the technical scheme of the application, firstly, through a simple physical salting-out process, supersaturated sodium chloride brine is used for precipitating sodium sulfonate, and the purity of the obtained sulfonate can be generally higher than 94%; then 8% aqueous solution of sulfonic acid and 8% aqueous solution of sodium hydroxide are obtained by double-stage membrane electrolysis, and the alkali liquor with low solubility can be applied to various accelerator production processes;
as the preferential selection, the biochemical effluent obtained by evaporating the aqueous solution of the sulfonic acid and the aqueous solution of the sodium hydroxide is used for dissolving the sulfonate, so that the biochemical effluent is effectively recycled, and the water system is ensured to be used mechanically without generating extra water.
The technical scheme of the application is that the byproduct sulfonic acid is applied to various industries including catalyst industry and the like. Meanwhile, the method does not adopt the traditional incineration process, has obvious control advantage on national carbon emission indexes, and is a low-carbon emission process.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A comprehensive treatment method of rubber accelerator byproduct sulfonate is characterized by comprising the following steps: 1) Cooling the residual wastewater discharged from the accelerator production unit to 25-40 ℃ for salting out;
2) Dissolving solid salt separated out by salt in water to prepare sulfonate aqueous solution with the mass concentration of 5-10%;
3) And (3) the sulfonate aqueous solution enters an electrolytic tank for electrolysis to obtain a sulfonate aqueous solution and a sodium hydroxide aqueous solution.
2. The method for comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 1, wherein the temperature in the step 1) is reduced to 30 ℃ for salting out.
3. The method for comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 1, wherein the salting-out process in the step 1) is to add supersaturated sodium chloride solution, and the sodium chloride content in the wastewater is ensured to be more than 24%.
4. The method for comprehensive treatment of rubber accelerator by-product sulfonate according to claim 1, wherein the aqueous solution of sulfonate with mass concentration of 8% is prepared in the step 2).
5. The method for the comprehensive treatment of the byproduct sulfonate of the rubber accelerator according to claim 1, wherein the electrolytic tank in the step 3) is a two-stage membrane electrolytic tank;
the two-stage membrane electrolytic cell comprises an electrolytic cell body, an anode and a cathode which are arranged at two sides of the electrolytic cell body, and a two-stage membrane unit which is arranged between the anode and the cathode; the two-stage membrane unit comprises a first two-stage membrane, an anion exchange membrane, a cation exchange membrane and a second two-stage membrane which are sequentially arranged from an anode to a cathode;
an anode chamber is formed between the anode and the first two-stage membrane; an acid chamber is formed between the first two-stage membrane and the anion exchange membrane, and a salt chamber is formed between the anion exchange membrane and the cation exchange membrane; an alkali chamber is formed between the cation exchange membrane and the second double-stage membrane; the second dual-stage membrane forms a cathode chamber with the cathode.
6. The method for comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 1, wherein the waste water discharged from the accelerator production unit in step 1) is derived from waste water generated in the preparation process of accelerator TBBS, accelerator CBS and accelerator DCBS.
7. The method for the comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 1, wherein the waste water discharged from the accelerator production unit in step 1) is derived from waste water generated in the preparation process of accelerator CBS;
the preparation process of the accelerator CBS comprises the following steps:
(a) Preparing an M-Na salt solution: mixing accelerator MBT with NaOH aqueous solution with mass concentration of 20% -35% to prepare M-Na salt solution;
wherein the mass ratio of the accelerator MBT to the NaOH aqueous solution is 1 (0.5-1.5), the mixing time is 0-2 h, and the mixing temperature is 40-60 ℃;
preparing an acid solution of cyclohexylamine: mixing cyclohexylamine with an acid solution with the mass concentration of 20-30% at 40-45 ℃ under the stirring condition to obtain an acid solution of cyclohexylamine;
wherein, the mol ratio of the cyclohexane to the solute in the acid solution is 1 (0.3-1), and the mass ratio of the cyclohexane to the acid solution is 1 (0.5-1);
(b) Introducing an M-Na salt solution, an acid solution of cyclohexylamine, a solvent and an oxidant solution into a microchannel reactor to perform oxidation reaction at 20-50 ℃, wherein the reaction residence time is 0.5-10 s;
wherein, the feeding mass ratio of the M-Na salt solution to the acid solution of the cyclohexylamine is 1 (1-2.5), the feeding mass ratio of the M-Na salt solution to the solvent is 1 (1.5-3), and the feeding mass ratio of the M-Na salt solution to the oxidant solution is 1 (1.2-4);
(c) The materials after oxidation are decompressed and evaporated to recycle the solvent under the conditions of 40 ℃ to 80 ℃ and the vacuum degree of 10kPa to 50kPa, and the rest is waste water after the CBS crude product is obtained by filtration.
8. The method for comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 7, wherein the acid solution is aqueous solution of hydrochloric acid, sulfuric acid or nitric acid; the solvent is one or a mixed solution of ethyl acetate and toluene; the oxidant is sodium hypochlorite.
9. The method for comprehensive treatment of rubber accelerator byproduct sulfonate according to claim 1, further comprising the step of 4) evaporating the aqueous solution of sulfonic acid and/or aqueous solution of sodium hydroxide to obtain pure sulfonic acid and/or sodium hydroxide; the evaporated water is used to dissolve the solid salt in step 2).
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CN104593812A (en) * | 2014-12-31 | 2015-05-06 | 山东天维膜技术有限公司 | Method for producing taurine by virtue of bipolar ion exchange membrane technology |
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CN1723299A (en) * | 2002-12-06 | 2006-01-18 | Om集团公司 | Electrolytic process for preparing metal sulfonates |
CN103787471A (en) * | 2014-01-24 | 2014-05-14 | 北京科技大学 | Device and method for processing sodium p-toluenesulfonate waste liquor |
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