CN105384964A - Method for processing waste residues in high content rubber antioxidant TMQ production process - Google Patents
Method for processing waste residues in high content rubber antioxidant TMQ production process Download PDFInfo
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- CN105384964A CN105384964A CN201510955858.8A CN201510955858A CN105384964A CN 105384964 A CN105384964 A CN 105384964A CN 201510955858 A CN201510955858 A CN 201510955858A CN 105384964 A CN105384964 A CN 105384964A
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- distillation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for processing waste residues in high content rubber antioxidant TMQ production process, the method is as follows: the waste residues are mixed with quantitative aniline, quantitative acetone and a quantitative monomer for dilution; reaction is performed at certain temperature for certain time; then a dilute alkaline solution is added dropwise, and a defoamer is added until no obvious bubble is in the solution; when the PH value reaches 6-7, the dropwise addition is stopped, and water is separated after standing; oil phase is transferred into a distillation kettle for monomer distillation for recovery of the monomer; the distillation is stopped when no reflux is observed by sight glass; after cooling, granulation is performed, softening point and active ingredient content are detected, and general antioxidant TMQ index requirements can be met. According to the method, by treatment of the waste residues in the high content rubber antioxidant TMQ production process, general antioxidant TMQ product indexes can be reached, hazardous solid waste production can be effectively reduced, and general antioxidant TMQ production cost can be reduced.
Description
Technical field
The invention belongs to the method for treatment of waste material of rubber ingredients, particularly a kind of high-content rubber antioxidant TMQ produce in the treatment process of waste residue.
Background technology
Rubber antioxidant TMQ is 2, the oligopolymer of 2,4-trimethylammonium-1,2-dihydroquinoline, the polymerization degree is 2-4, being a kind of ketone amines antioxidants, is faint yellow to amber powder or thin slice, is the outstanding especially class versatility amines antioxidants of heat resistanceheat resistant in rubber industry, oxygen aging performance, little with its toxicity, in rubber, consistency is good, and is widely used in producing radial and other rubber item, is one of rubber antioxidant product that domestic and international market has the call.Current commercially available prod is divided into coventional type anti-aging agent TMQ and high-content anti-aging agent TMQ.Common anti-aging agent TMQ bis-, three, tetramer content requirement is more than 40%, softening temperature 80-100 DEG C.
High-content rubber antioxidant TMQ bis-, three, tetramer content requirement reaches more than 80%, usually this production technique adopts two-step approach, first aniline and acetone carry out condensation and generate monomer, monomer is polymerized after purifying further again, generate 2-4 aggressiveness, as shown in Figure 1, aniline and catalyzer drop into polycondensation vessel in its Production Flow Chart, heat up, drip acetone and carry out condensation reaction.Via acetone, reaction water is taken out of.2,2,4-trimethylammonium-1,2-dihydroquinoline monomer (hereinafter referred to as monomer) steams and enters still kettle, further distilation by the follow-up temperature of continuing rising of reaction end.Monomer transfer after purification is polymerized under catalyst action to monomer polymerization still, generates 2-4 polymer, i.e. anti-aging agent TMQ effective constituent.Product is through neutralization, finished product of lowering the temperature to obtain.Because high-content TMQ is to product effective constituent, especially dimer content requires higher, repeatedly need be separated, purifies to monomer.Can at condensation kettle and still kettle generating portion residue after monomer separation, purification after condensation, circulation repeatedly needs periodic cleaning to produce solid waste afterwards.High-content TMQ per ton about produces 80kg waste residue, and a large amount of waste residue cannot process and contaminate environment.How being turned waste into wealth by waste material, the environmental issue solved in production process is problem to be solved by this invention.Analyzed through GC-MS by residue, residue main component is that intermediate product that boiling point is higher is as isopropyl aniline, anilino quinolines monomer, quinoline isomer, primary amine compound etc.
By analyzing and researching to residue composition, we adopt and residue and aniline, acetone are continued under certain condition to react to generate common anti-aging agent TMQ, realize turning waste into wealth, comprehensive utilization of resources.
Summary of the invention
The object of the present invention is to provide the treatment process of waste residue in a kind of high-content rubber antioxidant TMQ production process.Concrete technical scheme is as follows:
A treatment process for waste residue in high-content anti-aging agent TMQ production process, comprises the following steps:
(1) polycondensation: by residue and aniline recovery, reclaim acetone, 2,2,4-trimethylammonium-1,2-dihydroquinoline monomers according to mass ratio 1:(0.1-0.5): (2-5): the ratio of 0.1 mixes in a kettle., intensification polycondensation; Temperature of reaction 50-100 DEG C, reaction times 1-3h; By acetone Distillation recovery after reaction terminates; During reaction product is transferred to and still;
(2) neutralize: configuration quality concentration 5-10% basic solution; In dropping to and still, drip defoamer simultaneously; Stop when pH value reaches 6-7 dripping; After leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 200-250 DEG C; Stop distillation without during backflow in visor, cooling granulation obtains finished product.
Described basic solution comprises the strong alkaline substance such as sodium hydroxide, potassium hydroxide.
Described defoamer comprises high-carbon alcohols, polyethers, silicone based defoamer.
Because this flow process and coventional type anti-aging agent TMQ production technique are similar, coventional type anti-aging agent TMQ production line can be utilized to carry out recovery residue.
Detect its softening temperature and active constituent content, softening temperature reaches 80-100 DEG C, and effective constituent reaches more than 40%, and indices meets common anti-aging agent RD national standard.
By above means, can realize waste residue in high-content TMQ production process turns waste into wealth, and calculates, recyclable waste residue 800t by annual output 10000 tons of high-content TMQ, saves nearly 2,400,000 yuan of controlling waste residue cost; Produce common anti-aging agent TMQ900t, realize the new profit 5,000,000 yuan, environmental protection and remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1: high-content anti-aging agent TMQ production technological process;
Fig. 2: residue treatment process flow sheet.
Embodiment
Below in conjunction with accompanying drawing with by specific embodiment, the present invention is described in further detail:
As shown in Figure 1, 2: by reaction residues and quantitative recovery aniline in condensation kettle, still kettle in high-content TMQ production system, reclaim acetone, 2,2,4-trimethylammonium-1,2-dihydroquinoline monomer (hereinafter referred to as monomer) mixes intensification in a kettle. and carries out polycondensation.Maintenance certain temperature, time react.Reaction terminates recover acetone.During resultant is transferred to subsequently and still, drip dilute alkaline solution.Stop dripping when pH value arrives 6-7, and add defoamer extremely without obvious foam, point water after leaving standstill.Oil phase is transferred to still kettle and carries out monomer distillation.Visor stops distillation without during backflow.Granulation after leftover materials cooling, detect its softening temperature and active constituent content, softening temperature reaches 80-100 DEG C, and effective constituent reaches more than 40%, reaches anti-aging agent TMQ Standard.
Following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
(1) condensation: residue 100kg, aniline 10kg, acetone 200kg, monomer 10kg are mixed in a kettle., intensification polycondensation; Temperature of reaction 50 DEG C, reaction 3h; Reaction terminates acetone Distillation recovery;
(2) neutralize: configuration quality concentration 5% sodium hydroxide solution, drops to condensation kettle, drip silicone antifoam agent S909 extremely without obvious foam simultaneously; Stop dripping when pH value reaches 6, after leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 200 DEG C; Stop distillation without during backflow in visor, cooling granulation obtains finished product; Detect its softening temperature 92 DEG C, effective content reaches 43%, and indices meets common anti-aging agent RD national standard.
Embodiment 2
(1) condensation: residue 100kg, aniline 10kg, acetone 300kg, monomer 10kg are mixed in a kettle., intensification polycondensation.Temperature of reaction 75 DEG C, reaction 2h; Reaction terminates acetone Distillation recovery;
(2) neutralize: configuration quality concentration 7% potassium hydroxide solution, drops to condensation kettle, drip polyethers defoamer GP330 extremely without obvious foam simultaneously; Stop dripping when pH value reaches 7, after leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 230 DEG C.Stop distillation without during backflow in visor, cooling granulation obtains finished product; Detect its softening temperature 88 DEG C, effective content reaches 43%, and indices meets common anti-aging agent RD national standard.
Embodiment 3:
(1) condensation: residue 100kg, aniline 50kg, acetone 500kg, monomer 10kg are mixed in a kettle., intensification polycondensation; Temperature of reaction 100 DEG C, reaction 1h; Reaction terminates acetone Distillation recovery
(2) neutralize: configuration quality concentration 10% sodium hydroxide solution, drops to condensation kettle, drip higher alcohols defoamer 2,6-2,6-dimethyl-4-heptanol extremely without obvious foam simultaneously; Stop dripping when pH value reaches 7, after leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 250 DEG C.Stop distillation without during backflow in visor, cooling granulation obtains finished product; Detect its softening temperature 91 DEG C, effective content reaches 45%, and indices meets common anti-aging agent RD national standard.
Embodiment 4:
(1) condensation: residue 100kg, aniline 30kg, acetone 500kg, monomer 10kg are mixed in a kettle., intensification polycondensation; Temperature of reaction 100 DEG C, reaction 1h.Reaction terminates acetone Distillation recovery;
(2) neutralize: configuration quality concentration 10% potassium hydroxide solution, drops to condensation kettle, drip defoamer silicone antifoam agent S909 extremely without obvious foam simultaneously; Stop dripping when pH value reaches 7, after leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 250 DEG C.Stop distillation without during backflow in visor, cooling granulation obtains finished product.Detect its softening temperature 94 DEG C, effective content reaches 45%, and indices meets common anti-aging agent RD national standard.
Claims (3)
1. the treatment process of waste residue in high-content anti-aging agent TMQ production process, is characterized in that comprising the following steps:
(1) by residue and aniline recovery, reclaim acetone, 2,2,4-trimethylammonium-1,2-dihydroquinoline monomer is according to mass ratio 1:(0.1-0.5): (2-5): the ratio of 0.1 mixes in a kettle., temperature of reaction 50-100 DEG C, reaction times 1-3h; By acetone Distillation recovery after reaction terminates; During reaction product is transferred to and still;
(2) configuration quality concentration 5-10% basic solution; In dropping to and still, drip defoamer simultaneously; Stop when pH value reaches 6-7 dripping; After leaving standstill 30min, water layer is separated;
(3) oil phase enters monomer distillation still, distillation temperature 200-250 DEG C; Stop distillation without during backflow in visor, cooling granulation obtains finished product.
2. the method for claim 1, is characterized in that described basic solution liquid is the strong alkaline substance of sodium hydroxide, potassium hydroxide.
3. the method for claim 1, is characterized in that described defoamer is high-carbon alcohols, polyethers and silicone antifoam agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963965A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Recycling method of waste residue in antioxidant AW production |
| CN113087662A (en) * | 2019-12-23 | 2021-07-09 | 中石化南京化工研究院有限公司 | Method for removing impurity primary amine in anti-aging agent TMQ |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214640A (en) * | 2013-03-27 | 2013-07-24 | 科迈化工股份有限公司 | Production method of rubber antioxidant TMQ |
| CN103613537A (en) * | 2013-11-11 | 2014-03-05 | 河南省开仑化工有限责任公司 | Clean high-efficiency synthetic method of high-content anti-aging agent RD |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214640A (en) * | 2013-03-27 | 2013-07-24 | 科迈化工股份有限公司 | Production method of rubber antioxidant TMQ |
| CN103613537A (en) * | 2013-11-11 | 2014-03-05 | 河南省开仑化工有限责任公司 | Clean high-efficiency synthetic method of high-content anti-aging agent RD |
Non-Patent Citations (2)
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| 肖军: ""我国橡胶助剂三废治理述评"", 《化学工业》 * |
| 苏宏 等: ""橡胶防老剂RD生产废水处理方法研究"", 《烟台大学学报（自然科学与工程版）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963965A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Recycling method of waste residue in antioxidant AW production |
| CN110963965B (en) * | 2018-09-30 | 2022-10-18 | 中国石油化工股份有限公司 | Recycling method of waste residue in antioxidant AW production |
| CN113087662A (en) * | 2019-12-23 | 2021-07-09 | 中石化南京化工研究院有限公司 | Method for removing impurity primary amine in anti-aging agent TMQ |
| CN113087662B (en) * | 2019-12-23 | 2022-09-13 | 中石化南京化工研究院有限公司 | Method for removing primary amine impurities in anti-aging agent TMQ |
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