CN116283826A - Process method for efficiently recovering MBT from liquid resin - Google Patents
Process method for efficiently recovering MBT from liquid resin Download PDFInfo
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- CN116283826A CN116283826A CN202310072462.3A CN202310072462A CN116283826A CN 116283826 A CN116283826 A CN 116283826A CN 202310072462 A CN202310072462 A CN 202310072462A CN 116283826 A CN116283826 A CN 116283826A
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- 239000011347 resin Substances 0.000 title claims abstract description 113
- 229920005989 resin Polymers 0.000 title claims abstract description 113
- 239000007788 liquid Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000000047 product Substances 0.000 claims abstract description 44
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 196
- 239000000706 filtrate Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004448 titration Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a process method for efficiently recovering MBT from liquid resin. The invention comprises the following steps: s1, cooling and granulating liquid resin stripped with benzothiazole and sulfur (the liquid resin contains residual MBT) to obtain resin particles; s2, crushing the resin particles into resin powder; s3, mixing the resin powder and the dissolving agent, and heating for a period of time until the resin powder is completely dissolved to obtain a dissolving solution; s4, mixing and stirring the dissolution liquid and the reactant for a certain time, and standing and layering to obtain supernatant; s5, sequentially performing the steps of primary filtering, fine filtering, oxidizing, neutralizing, washing, dehydrating and drying on the supernatant to obtain the MBT product. The method can be used for efficiently recovering residual MBT in the liquid resin, so that the recovery yield of the recovered MBT product is high, the purity of the recovered MBT product is also high, the production cost is effectively reduced, and the method has good industrial application prospect.
Description
Technical Field
The invention relates to the field of rubber accelerator production, in particular to a process method for efficiently recovering MBT from liquid resin.
Background
The rubber accelerator MBT is a general accelerator, has the effect of quick vulcanization, has certain plasticity and aging resistance, and is widely applied to various rubber production. In addition, MBT is a main raw material for producing a sulfenamide accelerator such as CZ, NS, DZ, NOBS. The main method for producing the accelerator MBT at present is a high-pressure synthesis method, and the general yield is about 80-85% (calculated by aniline). The remainder is by-product benzothiazole, resinoid tar with unknown structure, etc., and these by-products are mixed with a small amount of water and are generally called liquid resin. The contents of benzothiazole, sulfur and accelerator MBT in the liquid resin are high, so that the treatment of dangerous waste not only causes great resource waste, but also affects the environment. At present, most enterprises extract benzothiazole and sulfur in liquid resin through steam stripping, but MBT in the liquid resin is difficult to recover practically, the recovery yield is low even if the MBT is recovered, and the purity and the initial melting point of the recovered MBT are poor.
Therefore, the invention provides the MBT high-efficiency recovery process method capable of efficiently recovering the MBT in the liquid resin.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a process method for efficiently recovering MBT from liquid resin.
The invention is realized by the following technical scheme:
a process method for efficiently recovering MBT from liquid resin comprises the following steps:
s1, cooling and granulating liquid resin stripped with benzothiazole and sulfur (the liquid resin contains residual MBT) to obtain resin particles;
s2, crushing the resin particles into resin powder;
s3, mixing the resin powder and the dissolving agent, and heating for a period of time until the resin powder is completely dissolved to obtain a dissolving solution;
s4, mixing and stirring the dissolution liquid and the reactant for a certain time, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, sequentially performing the steps of primary filtering, fine filtering, oxidizing, neutralizing, washing, dehydrating and drying on the supernatant to obtain the MBT product.
Preferably, in step S1, the particle diameter of the resin particles is 10 to 20mm. The particle size is too large to be smashed,
the pulverizing time is prolonged.
Preferably, in step S1, the particle diameter of the resin particles is 10 to 15mm.
Preferably, in step S2, the resin particles are pulverized into resin powder by a pulverizer, the pulverizing time being 5 to 15 minutes. The above-mentioned setting of crushing time is the crushing time of preferred, if crushing time is too long, rubbing and heating of the crusher causes the temperature to be high for the resin melts the bonding, influences crushing effect.
Preferably, in step S2, the pulverizing time is 5 to 10 minutes.
Preferably, in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, wherein the volume ratio of petroleum ether to ethylbenzene is 1 (1-3), and the petroleum ether is petroleum ether with the boiling range of 90-120 ℃. The above-mentioned dissolving agent can dissolve all of the resin powder.
Preferably, in step S3, the resin powder and the dissolving agent are mixed according to a mass ratio of 1 (5-10), and then heated to 60-90 ℃ for 60min, and the resin powder is completely dissolved.
Preferably, in step S4, the volume ratio of the dissolution solution to the reactant is 1: (2-5); the reactant is Ca (OH) 2 Solution, wherein Ca (OH) in the reactant 2 The mass fraction of (2-10%).
Preferably, in step S4, the reactants are selected from CaO and Ca (OH) 2 Ca (OH) prepared by adding water to one or two of the above materials 2 A solution.
Preferably, in the step S4, the dissolution solution and the reactant are mixed and stirred for 30-60 min, and the stirring speed is 100-200 r/min.
Preferably, in step S5, the supernatant is subjected to primary filtration to remove insoluble substances, fine filtration to remove micro-impurities, thereby obtaining a filtrate, then air or oxygen is introduced into the filtrate, meanwhile, a compound oxidant containing hydrogen peroxide is added dropwise for oxidation, then acid liquor is added dropwise for neutralization until the pH is 5-7, an MBT primary product is separated out, and then the MBT primary product is subjected to steps of washing, dewatering and drying in sequence, thereby obtaining an MBT product.
Preferably, in step S5, in the fine filtration process, the filler in the fine filter is activated carbon powder, activated carbon particles or carbon fibers.
Preferably, in step S5, the compound oxidant includes water, hydrochloric acid, hydrogen peroxide and 2, 6-tetramethylpiperidine oxide, and the mass ratio of the hydrogen peroxide to the 2, 6-tetramethylpiperidine oxide is 1000 (0.5-2.0).
Preferably, in step S5, the composite oxidizing agent is prepared by the following method: 2, 6-tetramethyl piperidine oxide is dissolved in hydrogen peroxide under the condition of stirring at 30-40 ℃, then clear water is added, and then hydrochloric acid is used for adjusting the pH value to 4.0-5.0, so that the composite oxidant is prepared.
Preferably, in step S5, the mass fraction of hydrogen peroxide in the composite oxidant is 5-15%.
Preferably, in the step S5, the acid liquid is hydrochloric acid, and the mass fraction of the hydrochloric acid is 2-10%;
preferably, in step S5, the mass fraction of the hydrochloric acid is 2-5%.
The beneficial effects of the invention are as follows:
1. the method for efficiently recovering the residual MBT in the liquid resin containing water, benzothiazole and resinoid tar with unknown structure has the advantages that the recovery yield of the MBT recovered from the liquid resin by adopting the efficient MBT recovery process method can reach more than 98%, the purity of the recovered MBT can reach more than 99%, and the production cost is effectively saved; the process method for efficiently recovering MBT from liquid resin can be used for industrial production-grade treatment, and 80 tons of liquid resin can be treated in one day; has good industrial application prospect;
2. the process method for efficiently recovering MBT from liquid resin has the advantages of simple process and easy operation;
3. the petroleum ether and ethylbenzene mixture is used as the dissolvent, so that the resin can be completely dissolved at a lower temperature, and the subsequent liquid-liquid phase contact reaction with the reactant is facilitated;
4. the invention adopts CaO and Ca (OH) 2 The reactant is prepared by adding water, so that the safety is high and the cost is lower.
Drawings
FIG. 1 is a process flow diagram of a process for efficiently recovering MBT from liquid resin according to the present invention.
Detailed Description
Example 1
A process method for efficiently recovering MBT from liquid resin specifically comprises the following steps:
s1, spraying 80 tons of stripped benzothiazole and sulfur liquid resin (the liquid resin contains residual MBT) into a granulator to form resin particles with the particle size of 10 mm;
s2, conveying the resin particles into a pulverizer to be pulverized for 5 minutes to obtain resin powder;
s3, putting 100kg of crushed resin powder and 500kg of dissolving agent into a dissolution kettle, heating to 60 ℃ and heating for 60min, and completely dissolving the resin powder to obtain a dissolution solution; in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, and the volume ratio of petroleum ether to ethylbenzene is 1:1;
s4, mixing 500L of the solution prepared in the step S3 with 1000L of Ca (OH) with the mass fraction of 2% prepared by CaO and water 2 Mixing the solutions, stirring for 30min at a stirring speed of 100r/min, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, primarily filtering the supernatant to remove insoluble substances to obtain filtrate, finely filtering the filtrate to further filter micro-impurities in the filtrate to obtain filtrate, introducing air or oxygen into the filtrate, simultaneously dropwise adding a compound oxidant with the mass fraction of 5% to oxidize, dropwise adding hydrochloric acid solution with the mass fraction of 2% to neutralize to pH value of 5, separating out an MBT primary product, and sequentially washing, dehydrating and drying the MBT primary product to obtain the MBT product.
In the first embodiment, the composite oxidant with the mass fraction of the hydrogen peroxide of 5% is prepared by the following method: 0.015kg of 2, 6-tetramethylpiperidine oxide is dissolved in 100kg of 30% hydrogen peroxide solution under stirring at 30 ℃, 485L of clear water is added, and 15L of 10% hydrochloric acid is used for regulating pH to 4.0, so as to prepare the composite oxidant with 5% dioxygen water mass fraction.
The test shows that the initial melting point of the MBT product recovered in the first embodiment is 176.5 ℃, which is 6.5 ℃ higher than the initial melting point of the MBT product in the national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT)); in addition, the purity titration method in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT) is used for testing the MBT product recovered in the first embodiment, and the purity of the MBT product recovered in the first embodiment is 99.4 percent;
furthermore, it was found by production that 80 tons of liquid resin raw material could be recovered and treated by the method described in example one, and 12177kg of MBT product could be recovered; before production, the present application also samples the liquid resin raw material stripped with benzothiazole and sulfur in step S1 of example 1, the sampling amount is 1g, then the sample is detected by using the purity titration method in national standard GB/T11407-2013, "vulcanization accelerator 2-Mercaptobenzothiazole (MBT)", and the detected amount of residual MBT in 1g of the liquid resin sample stripped with benzothiazole and sulfur is 0.155g, so that the conversion shows that in example one, the amount of residual MBT in 80 tons of liquid resin raw material should be 12400kg theoretically; thus, the recovery yield of example one of the present application should be 12177/12400=98.2%. Moreover, it is more notable that the 80 tons of liquid resin raw material in the first embodiment can be recovered only one day.
Example two
A process method for efficiently recovering MBT from liquid resin specifically comprises the following steps:
s1, spraying 80 tons of liquid resin stripped with benzothiazole and sulfur (the liquid resin contains residual MBT) into a granulator to form resin particles with the particle size of 12 mm;
s2, conveying the resin particles into a pulverizer to be pulverized for 7 minutes to obtain resin powder;
s3, putting 100kg of crushed resin powder and 700kg of dissolving agent into a dissolution kettle, heating to 70 ℃, and heating for 40min to completely dissolve the resin powder to obtain a dissolution solution; in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, and the volume ratio of petroleum ether to ethylbenzene is 1:2;
s4 mixing 500L of the solution prepared in the step S3 with 1500L of Ca (OH) 2 And 3% by mass of Ca (OH) in the water configuration 2 Mixing the solutions, stirring for 40min at a stirring speed of 150r/min, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, primarily filtering the supernatant to remove insoluble substances to obtain filtrate, finely filtering the filtrate to further filter micro-impurities in the filtrate to obtain filtrate, introducing air or oxygen into the filtrate, simultaneously dropwise adding a compound oxidant with the mass fraction of 8% to oxidize, dropwise adding hydrochloric acid solution with the mass fraction of 4% to neutralize to pH 6, separating out an MBT primary product, and sequentially washing, dehydrating and drying the MBT primary product to obtain the MBT product.
In the second embodiment, the composite oxidant with the mass fraction of 8% of hydrogen peroxide is prepared by the following method: 0.03kg of 2, 6-tetramethylpiperidine oxide is dissolved in 100kg of 30% hydrogen peroxide under stirring at 35 ℃, 265L of clear water is added, and 10L of 10% hydrochloric acid is used for regulating pH to 4.5, so as to prepare the composite oxidant with 8% of dioxygen water mass fraction.
The test shows that the initial melting point of the MBT product obtained by recycling in the second embodiment is 175.2 ℃, and is higher than the initial melting point of the MBT product in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT)) by 5.2 ℃; in addition, the purity titration method in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT) is used for testing the MBT product recovered in the second embodiment, and the purity of the MBT product recovered in the second embodiment is 99.2% through the test;
furthermore, it was also found by production that recovery of 80 tons of liquid resin feedstock by the method described in example two was able to recover 12425kg of MBT product; before production, the present application also samples the liquid resin raw material stripped with benzothiazole and sulfur in the second step S1, the sampling amount is 1g, then the sample is detected by using the purity titration method in national standard GB/T11407-2013, "vulcanization accelerator 2-Mercaptobenzothiazole (MBT)", and the detected amount of residual MBT in the 1g sample stripped with benzothiazole and sulfur is 0.158g, so that the conversion shows that in the second embodiment, the amount of residual MBT in 80 tons of liquid resin raw material should be 12640kg theoretically; thus, the recovery yield of example two of the present application should be 12425/12640=98.3%. Moreover, it is more notable that the 80 tons of liquid resin raw material in the second embodiment can be recovered only one day.
Example III
A process method for efficiently recovering MBT from liquid resin specifically comprises the following steps:
s1, spraying 80 tons of liquid resin stripped with benzothiazole and sulfur (the liquid resin contains residual MBT) into a granulator to form resin particles with the particle size of 13 mm;
s2, conveying the resin particles into a pulverizer for pulverizing for 10 minutes to obtain resin powder;
s3, putting 100kg of crushed resin powder and 900kg of dissolving agent into a dissolution kettle, and then heating to 80 ℃ for 50min to completely dissolve the resin powder; obtaining a dissolving solution; in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, and the volume ratio of petroleum ether to ethylbenzene is 1:3;
s4 mixing 500L of the solution prepared in the step S3 with 2000L of Ca (OH) with the mass fraction of 5% 2 Ca (OH) in combination with water 2 Mixing the solutions, stirring for 50min at the stirring speed of 200r/min, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, primarily filtering the supernatant to remove insoluble substances to obtain filtrate, finely filtering the filtrate to further filter micro-impurities in the filtrate to obtain filtrate, then introducing air or oxygen into the filtrate, simultaneously dropwise adding a compound oxidant with the mass fraction of 10% to oxidize, dropwise adding hydrochloric acid solution with the mass fraction of 5% to neutralize to pH 6 to precipitate an MBT primary product, and sequentially washing, dehydrating and drying the MBT primary product to obtain the MBT product.
In the third embodiment, the composite oxidant with the mass fraction of the hydrogen peroxide of 10% is prepared by the following method:
0.015kg of 2, 6-tetramethylpiperidine oxide is dissolved in 100kg of 30% hydrogen peroxide by mass fraction under stirring at 40 ℃, 192L of clear water is added, and 8L of 10% hydrochloric acid is used for regulating pH to 5.0, so as to prepare the composite oxidant with 10% dioxygen water by mass fraction.
The test shows that the initial melting point of the MBT product recovered in the third embodiment is 175.4 ℃, and is 5.4 ℃ higher than the initial melting point of the MBT product in the national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT)); in addition, the purity titration method in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT) is used for testing the MBT product recovered in the third embodiment, and the purity of the MBT product recovered in the third embodiment is 99.3% through the test;
furthermore, it was also found by production that 80 tons of liquid resin feedstock could be recovered by the method described in example three, enabling 12450kg of MBT product to be recovered; before production, the present application also samples the liquid resin raw material stripped with benzothiazole and sulfur in the third step S1, the sampling amount is 1g, then the sample is detected by using the purity titration method in national standard GB/T11407-2013, "vulcanization accelerator 2-Mercaptobenzothiazole (MBT)", and the detected amount of residual MBT in the sample of 1g of the liquid resin stripped with benzothiazole and sulfur is 0.158g, so that the conversion shows that in the third embodiment, the amount of residual MBT in 80 tons of liquid resin raw material should be 12640kg theoretically; thus, the recovery yield of example three of the present application should be 12450/12640=98.5%. Moreover, it is more notable that the 80 tons of liquid resin raw material in the third embodiment also requires only one day to complete the recovery treatment process.
Example IV
A process method for efficiently recovering MBT from liquid resin specifically comprises the following steps:
s1, spraying 80 tons of liquid resin stripped with benzothiazole and sulfur (the liquid resin contains residual MBT) into a granulator to form resin particles with the particle size of 15 mm;
s2, conveying the resin particles into a pulverizer to be pulverized for 10 minutes to obtain resin powder;
s3, putting 100kg of crushed resin powder and 1000kg of dissolving agent into a dissolution kettle, heating to 80 ℃, and heating for 60min to completely dissolve the resin powder to obtain a dissolution solution; in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, and the volume ratio of petroleum ether to ethylbenzene is 1:3;
s4, reacting 500L of the solution prepared in the step S3 with 2500L of Ca (OH) with CaO and water to prepare the calcium carbonate (Ca-OH) with the mass fraction of 10 percent 2 Mixing the solutions, mixing for 60min under the condition of stirring speed of 150r/min, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, primarily filtering the supernatant to remove insoluble substances to obtain filtrate, finely filtering the filtrate to further filter micro-impurities in the filtrate to obtain filtrate, then introducing air or oxygen into the filtrate, simultaneously dropwise adding a compound oxidant with the mass fraction of hydrogen peroxide of 15% for oxidation, dropwise adding hydrochloric acid solution with the mass fraction of 5% for neutralization until the pH value is 6, and separating out an MBT primary product; and then, sequentially washing, dehydrating and drying the MBT primary product to obtain the MBT product.
In the fourth embodiment, the compound oxidant with the mass fraction of the hydrogen peroxide of 15% is prepared by the following method:
0.045kg of 2, 6-tetramethylpiperidine oxide is dissolved in 100kg of 30% hydrogen peroxide under the condition of stirring at 30 ℃, 95L of clear water is added, and then the pH value is adjusted to 5.0 by 5L of 10% hydrochloric acid, so as to prepare the composite oxidant with 15% of dioxygen water mass fraction.
The test shows that the initial melting point of the MBT product recovered in the fourth embodiment is 175.1 ℃, and compared with the initial melting point of the MBT product in the national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT)), the initial melting point of the MBT product is 170.0 ℃ and is 5.1 ℃ higher; in addition, the purity of the MBT product recovered in the fourth embodiment is 99.1% as proved by testing the MBT product recovered in the fourth embodiment by a purity titration method in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT));
furthermore, it was found by production that 12595kg of MBT product could be recovered by recovery of 80 tons of liquid resin feedstock by the method described in example four; before production, the liquid resin raw material stripped with benzothiazole and sulfur in the fourth step S1 is sampled, the sampling amount is 1g, then the purity titration method in national standard GB/T11407-2013 (vulcanization accelerator 2-Mercaptobenzothiazole (MBT)) is used for detection, and the detected residual MBT amount in 1g of the liquid resin raw material stripped with benzothiazole and sulfur is 0.160g, so that the conversion shows that in the fourth step, the residual MBT amount in 80 tons of the liquid resin raw material is 12800kg theoretically; thus, the recovery yield of example four of the present application should be 12595/12800=98.4%. Moreover, it is more notable that the 80 tons of liquid resin raw material in the fourth embodiment also requires only one day to complete the recovery process.
The present invention has been described by way of the above embodiments, but the present invention is not limited to the above embodiments, and any modification or variation based on the present invention falls within the scope of the present invention as claimed.
Claims (10)
1. A process method for efficiently recovering MBT from liquid resin is characterized by comprising the following steps: the method comprises the following steps: s1, cooling and granulating the liquid resin stripped with benzothiazole and sulfur to obtain resin particles;
s2, crushing the resin particles into resin powder;
s3, mixing the resin powder and the dissolving agent, and heating for a period of time until the resin powder is completely dissolved to obtain a dissolving solution; s4, mixing and stirring the dissolution liquid and the reactant for a certain time, standing for layering to obtain supernatant, and finishing the back extraction process;
s5, sequentially performing the steps of primary filtering, fine filtering, oxidizing, neutralizing, washing, dehydrating and drying on the supernatant to obtain the MBT product.
2. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in step S1, the particle diameter of the resin particles is 10 to 20mm.
3. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in step S2, the resin particles are pulverized into resin powder by a pulverizer for 5 to 15 minutes.
4. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in the step S3, the solvent is a mixture of petroleum ether and ethylbenzene, wherein the volume ratio of petroleum ether to ethylbenzene is 1 (1-3), and the petroleum ether is petroleum ether with the boiling range of 90-120 ℃.
5. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in the step S3, the resin powder and the dissolvent are mixed according to the mass ratio of 1 (5-10), then heated to 60-90 ℃ for 40-60 min, and the resin powder is completely dissolved.
6. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in the step S4, the volume ratio of the dissolution solution to the reactant is 1: (2-5); the reactant is Ca (OH) 2 Solution, wherein Ca (OH) in the reactant 2 The mass fraction of (2-10%).
7. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in the step S4, the reactants are CaO and Ca (OH) 2 Ca (OH) prepared by adding water to one or two of the above materials 2 A solution.
8. The process for efficiently recovering MBT from liquid resin according to claim 1, wherein: in the step S5, the supernatant is subjected to primary filtration to remove insoluble substances, and fine filtration to remove micro impurities, so as to obtain filtered liquid; and introducing air or oxygen into the filtered clear liquid, simultaneously dropwise adding a compound oxidant containing hydrogen peroxide for oxidation, dropwise adding acid liquor for neutralization until the pH value is 5-7, separating out an MBT primary product, and sequentially washing, dehydrating and drying the MBT primary product to obtain the MBT product.
9. The process for efficiently recovering MBT from liquid resin according to claim 8, wherein: in the step S5, the compound oxidant containing hydrogen peroxide comprises water, hydrochloric acid, hydrogen peroxide and 2, 6-tetramethylpiperidine oxide, wherein the mass ratio of the hydrogen peroxide to the 2, 6-tetramethylpiperidine oxide is 1000 (0.5-2.0).
10. A process for the efficient recovery of MBT from liquid resins according to claim 8 or 9, characterized in that: the compound oxidant containing hydrogen peroxide is prepared by the following method: 2, 6-tetramethyl piperidine oxide is dissolved in hydrogen peroxide under the condition of stirring at 30-40 ℃, then clear water is added, and then hydrochloric acid is used for adjusting the pH value to 4.0-5.0, so that the composite oxidant is prepared.
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