CN1085224C - Process for desulfurizing used rubber - Google Patents
Process for desulfurizing used rubber Download PDFInfo
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- CN1085224C CN1085224C CN99115013A CN99115013A CN1085224C CN 1085224 C CN1085224 C CN 1085224C CN 99115013 A CN99115013 A CN 99115013A CN 99115013 A CN99115013 A CN 99115013A CN 1085224 C CN1085224 C CN 1085224C
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- waste rubber
- sweetening agent
- desulfurization
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Abstract
The present invention discloses a method for desulphurizing waste rubber. A desulfurizing agent which is prepared from mono aromatics, organic acid, metal chloride and mineral acid is uniformly mixed with waste rubber according to a certain proportion, the desulfurizing agent and the waste rubber react at 10 to 150 DEG C for 0.1 to 200 hours, and then, the waste rubber can be effectively desulfurized. The method for desulphurizing waste rubber has the advantages of easy operation, low desulfurizing reaction temperature, favorable and uniform desulfurizing effect, low toxicity of the desulfurizing agent, small environmental pollution, etc.
Description
The invention belongs to the reclaimed rubber production technical field, be specifically related to a kind of method that adopts pharmaceutical chemicals to make the waste rubber desulfurization.
Along with the raising of social development degree, the increase of rubber-consumer amount, though the generation of waste rubber is a lot, the material that waste rubber is had many uses through changing into after regenerating, use value is higher.Traditional technique for regenerated rubber flow process is: waste rubber → cut glue → washing → coarse breaking → fine crushing → sieve → separated fiber and metal sundries → desulfurization → cleaning → setting-out → drying → kneading → filter glue → freshening → refining → slice finished product.Desulfurization process wherein then is a key link in the reclaimed rubber production process, is the key that influences the reclaimed rubber quality product.
Adopt pharmaceutical chemicals that waste rubber is carried out desulfurization, China commonly used oil process, water/oil method etc. are arranged.Though oil process is relative with the toxicity of the sweetening agent of its use of water/oil method less, but the temperature height of its desulfurization, oil process are 160~170 ℃, and water/oil method is 180~190 ℃, and under high like this temperature, also reach heat-up time about 10 hours respectively and 2~4 hours (" rubber industry handbook " first, Chemical Industry Press, 1989, P1052~1053), obviously, high temperature will cause the cross-linked rubber degraded excessively for a long time, and is bigger to the rubber molecular chain infringement.
The seventies, the patent (CA84:45783h and CA93:48281q) that Japan and Sweden have applied for the normal temperature doctor treatment in succession, what its sweetening agent adopted is phenylhydrazine-iron protochloride.The advantage of this method is desulfurization at normal temperatures, and shortcoming is that phenylhydrazine toxicity is big, price is high, and the desulfurization degree is inhomogeneous, and effect is relatively poor.
The objective of the invention is to overcome the problem that prior art exists, intend providing that a kind of desulfurization temperature is low, sweetening effectiveness good and easy and simple to handle, the waste rubber sulfur method of the nontoxic substantially or low toxicity of employed sweetening agent component.
The objective of the invention is to reach by a kind of like this technical scheme: with proportion by weight is mononuclear aromatics 100, organic acid 0.1~50, metal chloride 0~30, mineral acid 0~10 mixes the sweetening agent of being formed, mass ratio by waste rubber and sweetening agent is 100: (10~1500), add in the waste rubber, and mix, reaction can make the waste rubber desulfurization in 0.1~200 hour effectively, equably under 10~150 ℃.
Sweetening agent also can directly add in the waste rubber stirring desulphurization together by proportioning again.
Wherein the mononuclear aromatics that uses of sweetening agent can be benzene or toluene or dimethylbenzene, and perhaps the mixture of any two or three kinds in them comprises without fractionation rough crude benzol or light oil.
Employed organic acid can be formic acid or acetate or sulfonic acid or phenylformic acid or Mono Chloro Acetic Acid or any two or two or more mixtures in them in the sweetening agent, and its optimum amount ranges is 1~30 part.
Employed metal chloride can be zinc chloride or iron(ic) chloride or aluminum chloride or the mixture of any two or three kinds in them in the sweetening agent, and its optimum amount ranges is 0~5 part.
The mineral acid that sweetening agent uses is sulfuric acid or hydrogenchloride, and its optimum amount ranges is 0~5 part.
In above-mentioned technical scheme, if take all factors into consideration speed of response and sweetening effectiveness, the optimum proportioning of its waste rubber and sweetening agent is 100 by mass parts: (300~1000); Optimum desulfurization temperature is 40~100 ℃; Optimum desulfurization time is 2~12 hours.When specifically selecting process control parameter, general selection principle is then desulfurization time weak point of desulfurization temperature height, and desulfurization temperature is low, and then desulfurization time is long partially.
The waste rubber that supplies desulfurization to use can be processed into rubber powder by existing waste rubber pulverizing technology and just carry out desulfurization, also can use the work in-process sizing material of scrapping in scrap rubber sheet or the rubber plant directly to carry out desulfurization.Waste rubber after the desulfurization carries out machining processes by the Production Flow Chart of conventional regeneration glue, and unreacted mononuclear aromatics and acetate or formic acid can reclaim with well-known distillation condensation technology in the system, reuses.
Compared with the prior art the present invention has the following advantages:
1. because sulfur method provided by the present invention is to carry out at normal temperatures or high slightly temperature was finished in the short period of time basically, can reduce destruction, guarantee the reclaimed rubber quality product rubber molecular chain.
2. the necessary component mononuclear aromatics toxicity of the selected sweetening agent of the present invention is lower, and organic acid is nontoxic substantially, and temperature of reaction is lower in addition, therefore can reduce the pollution to environment.
3. because the mononuclear aromatics of selecting for use is the fine solvent of rubber, can be rapidly abundant swollen rubber, the reactant diffusion profile is even, can guarantee that not only waste rubber grain is inner consistent with the desulfurization degree of appearance, and the stress of swelling generation also helps promoting the fracture of cross-link bond, so sulfur method of the present invention can use thicker rubber powder or scrap rubber sheet.
4. method provided by the present invention is very simple and easy to do, and only need stir gets final product, and sweetener is not had requirement yet.
Provide embodiment below, so that the invention will be further described.
Embodiment one:
1. prepare sweetening agent with 100 parts of toluene, 20 parts of acetate, 5 parts of zinc chloride, stirring at normal temperatures gets final product.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 500, be dipped in the sweetening agent, fully stir, and in 45 ℃ of reactions 10 hours down, desulfurization effectively.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.64 * 10
-5Mol/g has reduced by 90.7%.
Embodiment two:
1. prepare sweetening agent with 100 parts of toluene, 15 parts of acetate, 5 parts in iron(ic) chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 500, be dipped in the sweetening agent, fully stir, 45 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.77 * 10
-5Mol/g has reduced by 88.8%.
Embodiment three:
1. prepare sweetening agent with 100 parts of benzene, 20 parts of acetate, 2 parts in aluminum chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 800, be dipped in the sweetening agent, fully stir, 50 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.79 * 10
-5Mol/g has reduced by 88.5%.
Embodiment four:
1. prepare sweetening agent with 100 parts of benzene, 20 parts of acetate, 2 parts in iron(ic) chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 800, be dipped in the sweetening agent, fully stir, 50 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.60 * 10
-5Mol/g has reduced by 91.2%.
Embodiment five:
1. prepare sweetening agent with 50 parts of benzene, 50 parts of toluene, 8 parts in phenylformic acid, 2 parts of zinc chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1000, be dipped in the sweetening agent, fully stir, 50 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.63 * 10
-5Mol/g has reduced by 90.8%.
Embodiment six:
1. prepare sweetening agent with 100 parts of toluene, 10 parts of Mono Chloro Acetic Acids, 2 parts of zinc chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 600, be dipped in the sweetening agent, fully stir, 50 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.94 * 10
-5Mol/g has reduced by 86.3%.
Embodiment seven:
1. prepare sweetening agent with 50 parts of benzene, 50 parts of toluene, 12 parts in phenylformic acid, 2 parts of zinc chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1000, be dipped in the sweetening agent, fully stir, 80 ℃ of reactions 4 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.88 * 10
-5Mol/g has reduced by 87.2%.
Embodiment eight:
1. prepare sweetening agent with 100 parts of toluene, 10 parts of acetate, 5 parts in formic acid, 2 parts of zinc chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1000, be dipped in the sweetening agent, fully stir, 80 ℃ of reactions 4 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.86 * 10
-5Mol/g has reduced by 87.4%.
Embodiment nine:
1. prepare sweetening agent with 50 parts of benzene, 50 parts of toluene, 5 parts of tosic acid, 2 parts of zinc chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 600, be dipped in the sweetening agent, fully stir, 50 ℃ of reactions 10 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 1.08 * 10
-5Mol/g has reduced by 84.2%.
Embodiment ten:
1. prepare sweetening agent with 100 parts of dimethylbenzene, 10 parts of acetate, 1 part in sulfuric acid, 1 part of zinc chloride, 0.5 part in iron(ic) chloride, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1000, be dipped in the sweetening agent, fully stir, 100 ℃ of reactions 2 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 0.90 * 10
-5Mol/g has reduced by 86.9%.
Embodiment 11:
1. prepare sweetening agent with 50 parts of benzene, 50 parts of toluene, 20 parts of acetate, 5 parts of tosic acid, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1200, be dipped in the sweetening agent, fully stir, 24 ℃ of reactions 144 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 1.75 * 10
-5Mol/g has reduced by 74.5%.
Embodiment 12:
1. prepare sweetening agent with 100 parts of toluene, 15 parts of acetate, 10 parts in formic acid, it is standby to stir at normal temperatures.
Desulphurization reaction with waste rubber by with the proportioning of sweetening agent 100: 1200, be dipped in the sweetening agent, fully stir, 24 ℃ of reactions 168 hours down.
The cross-link bond density of waste rubber is 6.85 * 10 before the present embodiment desulfurization
-5Mol/g, the cross-link bond density after the desulfurization is 1.16 * 10
-5Mol/g has reduced by 83.1%.
Claims (6)
1. the sulfur method of a waste rubber adds sweetening agent in the waste rubber by proportioning, it is characterized in that:
1) composition of sweetening agent is a mononuclear aromatics 100 by proportion by weight, organic acid 0.1~50, metal chloride 0~30, mineral acid 0~10;
2) mass ratio of waste rubber and sweetening agent is 100: (10~1500), and mix, reacted 0.1~200 hour down at 10~150 ℃.
2. the sulfur method of waste rubber according to claim 1 is characterized in that employed mononuclear aromatics is benzene or toluene or dimethylbenzene in the sweetening agent, and perhaps the mixture of any two or three kinds in them comprises without fractionation purified crude benzol or light oil.
3. the sulfur method of waste rubber according to claim 1, it is characterized in that employed organic acid in the sweetening agent is formic acid or acetate or sulfonic acid or phenylformic acid or Mono Chloro Acetic Acid or any two or two or more mixtures in them, its amount ranges is 1~30 part.
4. the sulfur method of waste rubber according to claim 1 is characterized in that in the sweetening agent that employed metal chloride is zinc chloride or iron(ic) chloride or aluminum chloride or any two or two or more mixtures in them, and its amount ranges is 0~5 part.
5. the sulfur method of waste rubber according to claim 1 is characterized in that mineral acid is sulfuric acid or hydrogenchloride, and its amount ranges is 0~5 part.
6. according to the sulfur method of claim 1 or 2 or 3 or 4 or 5 described waste rubbers, it is characterized in that the proportioning of waste rubber and sweetening agent is 100 by mass parts: (300~1000); Desulfurization temperature is 40~100 ℃; Desulfurization time is 2~12 hours.
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CN99115013A CN1085224C (en) | 1999-07-15 | 1999-07-15 | Process for desulfurizing used rubber |
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CN99115013A CN1085224C (en) | 1999-07-15 | 1999-07-15 | Process for desulfurizing used rubber |
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CN1281000A CN1281000A (en) | 2001-01-24 |
CN1085224C true CN1085224C (en) | 2002-05-22 |
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CN103044735B (en) * | 2012-12-06 | 2014-12-10 | 开平市康汇橡胶制品有限公司 | Method for producing regenerated rubber |
CN104629085A (en) * | 2015-01-30 | 2015-05-20 | 柳州市中配橡塑配件制造有限公司 | Method for desulfurizing waste rubber |
CN105037792B (en) * | 2015-07-03 | 2017-12-19 | 李晓武 | A kind of preparation method of acrylate reclaimed rubber |
CN106009725A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Odorless waste tire rubber powder modifying agent easy to melt |
CN106009726A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Asphalt modified with odorless rubber powder easy to melt |
CN106009729A (en) * | 2016-06-28 | 2016-10-12 | 郭迎庆 | Preparing method of modified emulsified asphalt |
CN106118099A (en) * | 2016-07-13 | 2016-11-16 | 吴迪 | A kind of preparation method of environment protection modified pitch |
CN106867022A (en) * | 2017-02-06 | 2017-06-20 | 成都新火环保科技有限公司 | A kind of scrap rubber regenerative agent and preparation method thereof |
CN107236188A (en) * | 2017-06-26 | 2017-10-10 | 湖北大学 | A kind of modified waste rubber powder and pp intermingling materials and preparation method thereof |
CN107177099B (en) * | 2017-06-26 | 2022-02-22 | 湖北大学 | Modified waste rubber powder and modified PP (polypropylene) blended material and preparation method thereof |
CN108395573A (en) * | 2018-03-09 | 2018-08-14 | 福州大学 | A kind of biodegrading process of vulcanized rubber selectivity rupture crosslinks network |
CN109535750A (en) * | 2018-12-03 | 2019-03-29 | 江苏东道交通科技集团有限公司 | A kind of rubber asphalt stabilizer and preparation method thereof |
CN109593235A (en) * | 2018-12-03 | 2019-04-09 | 江苏东道交通科技集团有限公司 | A kind of rubber asphalt effectively keeps the temperature additive and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1052125A (en) * | 1990-12-15 | 1991-06-12 | 孙鹏恭 | Rapid desulfurization method for waste rubber strips |
CN1145295A (en) * | 1995-09-13 | 1997-03-19 | 南通市回力橡胶实业总公司 | Regenerated rubber for fined tyre and its prodn. tech. |
-
1999
- 1999-07-15 CN CN99115013A patent/CN1085224C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1052125A (en) * | 1990-12-15 | 1991-06-12 | 孙鹏恭 | Rapid desulfurization method for waste rubber strips |
CN1145295A (en) * | 1995-09-13 | 1997-03-19 | 南通市回力橡胶实业总公司 | Regenerated rubber for fined tyre and its prodn. tech. |
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