CN105384964B - The processing method of waste residue in high content rubber antioxidant TMQ productions - Google Patents
The processing method of waste residue in high content rubber antioxidant TMQ productions Download PDFInfo
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- CN105384964B CN105384964B CN201510955858.8A CN201510955858A CN105384964B CN 105384964 B CN105384964 B CN 105384964B CN 201510955858 A CN201510955858 A CN 201510955858A CN 105384964 B CN105384964 B CN 105384964B
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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 kind of processing method of waste residue in high content rubber antioxidant TMQ production processes, its process includes：By residue and quantitative aniline, acetone, monomer mixed diluting.Certain temperature is maintained, the time is reacted.Dilute alkaline solution is then added dropwise, and adds defoamer to without obvious foam.Stop being added dropwise when pH value reaches 67, divide water after standing.Oil phase is transferred to distillation still and carries out monomer distillation recovery monomer.Stop distillation when visor is without backflow.It is granulated after cooling, detects its softening point and active constituent content, meets common age resistor TMQ index request.Caused residue in high content TMQ production processes by processing, is reached common age resistor TMQ product index, can effectively reduce dangerous solid waste and produce, while can reduce common age resistor TMQ production costs by this method.
Description
Technical field
The invention belongs to the method for treatment of waste material of rubber chemicals, more particularly to a kind of high content rubber antioxidant TMQ productions
The processing method of middle waste residue.
Background technology
Rubber antioxidant TMQ is the oligomer of 2,2,4- trimethyl -1,2- EEDQs, degree of polymerization 2-4, is a kind of ketone
Amines antioxidants, it is faint yellow to amber powder or thin slice, be that heat resistanceheat resistant in rubber industry, oxidative aging can be especially outstanding one
Class versatility amines antioxidants, with its small toxicity, compatibility is good in rubber, and is widely used in producing radial and its
Its rubber, it is one of rubber antioxidant product being had the call on domestic and international market.Presently commercially available product is divided into commonly
Type age resistor TMQ and high content age resistor TMQ.Common age resistor TMQ bis-, three, tetramer content requirement are more than 40%, softening
80-100 DEG C of point.
Up to more than 80%, the usual production technology uses for high content rubber antioxidant TMQ bis-, three, tetramer content requirement
Two-step method, first aniline carry out condensation generation monomer with acetone, and monomer is polymerize after further purification again, and generation 2-4 gathers
Body, its production procedure heating, are added dropwise acetone and carry out condensation reaction as shown in figure 1, aniline and catalyst input polycondensation vessel.Via
Acetone takes reaction water out of.Reaction terminates follow-up temperature of continuing rising, and 2,2,4- trimethyl -1,2- EEDQs monomers is (hereinafter referred to as single
Body) steam into distillation still, further distilation.Monomer after purification is transferred to monomer polymeric kettle and issued in catalyst action
Raw polymerization, generates 2-4 condensates, i.e. age resistor TMQ active ingredients.Product is neutralized, cool to obtain finished product.Due to high content TMQ
Higher is required to product active ingredient, especially dimer content, monomer need to repeatedly be separated, purified.It is single after condensation
Part residue can be produced in condensation kettle and distillation still after body separation, purification, need periodic cleaning to produce solid waste after circulation repeatedly.It is per ton
High content TMQ about produces 80kg waste residues, and a large amount of waste residues cannot handle and pollute environment.How waste material to be turned waste into wealth, solve life
Environmental issue during production is problem to be solved by this invention.Residue is analyzed through GC-MS, residue main component is
The higher intermediate product of boiling point such as isopropyl aniline, anilino quinolines monomer, quinoline isomers, primary amine compound etc..
By being analyzed and researched to residue composition, we use continues residue and aniline, acetone under certain condition
Reaction is to generate common age resistor TMQ, and realization is turned waste into wealth, comprehensive utilization of resources.
The content of the invention
It is an object of the invention to provide a kind of processing method of waste residue in high content rubber antioxidant TMQ production processes.
Concrete technical scheme is as follows：
The processing method of waste residue, comprises the following steps in a kind of high content age resistor TMQ production processes：
(1) polycondensation：By residue and aniline recovery, recovery acetone, 2,2,4- trimethyl -1,2- EEDQ monomers according to matter
Measure ratio 1:(0.1-0.5):(2-5):0.1 ratio is mixed in a kettle, and heat up polycondensation；50-100 DEG C of reaction temperature,
Reaction time 1-3h；Acetone is distilled to recover by reaction after terminating；Reaction product is transferred to neutralization kettle；
(2) neutralize：Configuration quality concentration 5-10% alkaline solutions；Neutralization kettle is added dropwise to, while defoamer is added dropwise；Work as pH value
Stop being added dropwise when reaching 6-7；Water layer is separated after standing 30min；
(3) oil phase enters monomer distillation kettle, 200-250 DEG C of vapo(u)rizing temperature；Stop distillation when in visor without backflow, cooling is made
Grain obtains finished product.
The alkaline solution includes the strong alkaline substances such as sodium hydroxide, potassium hydroxide.
The defoamer includes high-carbon alcohols, polyethers, organic silicon defoamer.
Because this flow is similar with plain edition age resistor TMQ production technologies, enter using plain edition age resistor TMQ production lines
Row recovery residue.
Its softening point and active constituent content are detected, softening point reaches 80-100 DEG C, and active ingredient is every up to more than 40%
Index meets common anti-aging agent RD national standard.
By above means, waste residue in high content TMQ production processes, which can be achieved, turns waste into wealth, by 10,000 tons of high contents of annual output
TMQ is calculated, recyclable waste residue 800t, saves nearly 2,400,000 yuan of controlling waste residue cost；Common age resistor TMQ900t is produced, is realized new
Increase 5,000,000 yuan of profit, environmental protection and remarkable in economical benefits.
Brief description of the drawings
Fig. 1:High content age resistor TMQ production technological process；
Fig. 2:Residue treatment process chart.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings and by specific embodiment：
As shown in Figure 1, 2：By reaction residues and quantitative recovery benzene in condensation kettle, distillation still in high content TMQ production systems
Amine, recovery acetone, 2,2,4- trimethyl -1,2- EEDQs monomers (hereinafter referred to as monomer) mix heating and carried out in a kettle
Polycondensation reaction.Certain temperature, time is maintained to be reacted.Reaction terminates acetone recovery.Subsequently generate thing and be transferred to neutralization kettle, drip
Adding dilute alkali property solution.Stop being added dropwise when pH value reaches 6-7, and add defoamer to without obvious foam, divide water after standing.Oil phase
It is transferred to distillation still and carries out monomer distillation.Stop distillation when visor is without backflow.It is granulated after leftover materials cooling, detects its softening point
With active constituent content, softening point reaches 80-100 DEG C, and active ingredient reaches age resistor TMQ Standards up to more than 40%.
Following examples can make those skilled in the art that the present invention be more completely understood, but not limit this in any way
Invention.
Embodiment 1
(1) it is condensed：Residue 100kg, aniline 10kg, acetone 200kg, monomer 10kg are mixed in a kettle, risen
Warm polycondensation；50 DEG C of reaction temperature, react 3h；Reaction terminates acetone being distilled to recover；
(2) neutralize：The sodium hydroxide solution of configuration quality concentration 5%, is added dropwise to condensation kettle, while organic silicon defoamer is added dropwise
S909 is to without obvious foam；Stop being added dropwise when pH value reaches 6, separate water layer after standing 30min；
(3) oil phase enters monomer distillation kettle, 200 DEG C of vapo(u)rizing temperature；Stop distillation when in visor without backflow, cooling is granulated
Finished product；92 DEG C of its softening point is detected, for effective content up to 43%, indices meet common anti-aging agent RD national standard.
Embodiment 2
(1) it is condensed：Residue 100kg, aniline 10kg, acetone 300kg, monomer 10kg are mixed in a kettle, risen
Warm polycondensation.75 DEG C of reaction temperature, react 2h；Reaction terminates acetone being distilled to recover；
(2) neutralize：The potassium hydroxide solution of configuration quality concentration 7%, is added dropwise to condensation kettle, while polyethers defoamer is added dropwise
GP330 is to without obvious foam；Stop being added dropwise when pH value reaches 7, separate water layer after standing 30min；
(3) oil phase enters monomer distillation kettle, 230 DEG C of vapo(u)rizing temperature.Stop distillation when in visor without backflow, cooling is granulated
Finished product；88 DEG C of its softening point is detected, for effective content up to 43%, indices meet common anti-aging agent RD national standard.
Embodiment 3：
(1) it is condensed：Residue 100kg, aniline 50kg, acetone 500kg, monomer 10kg are mixed in a kettle, risen
Warm polycondensation；100 DEG C of reaction temperature, react 1h；Reaction terminates acetone being distilled to recover
(2) neutralize：The sodium hydroxide solution of configuration quality concentration 10%, is added dropwise to condensation kettle, while higher alcohols defoaming is added dropwise
Agent 2,6- 2,6-dimethyl-4-heptanols are to without obvious foam；Stop being added dropwise when pH value reaches 7, separate water layer after standing 30min；
(3) oil phase enters monomer distillation kettle, 250 DEG C of vapo(u)rizing temperature.Stop distillation when in visor without backflow, cooling is granulated
Finished product；91 DEG C of its softening point is detected, for effective content up to 45%, indices meet common anti-aging agent RD national standard.
Embodiment 4：
(1) it is condensed：Residue 100kg, aniline 30kg, acetone 500kg, monomer 10kg are mixed in a kettle, risen
Warm polycondensation；100 DEG C of reaction temperature, react 1h.Reaction terminates acetone being distilled to recover；
(2) neutralize：The potassium hydroxide solution of configuration quality concentration 10%, is added dropwise to condensation kettle, while it is organic that defoamer is added dropwise
Silicon defoaming agent S909 is to without obvious foam；Stop being added dropwise when pH value reaches 7, separate water layer after standing 30min；
(3) oil phase enters monomer distillation kettle, 250 DEG C of vapo(u)rizing temperature.Stop distillation when in visor without backflow, cooling is granulated
Finished product.94 DEG C of its softening point is detected, for effective content up to 45%, indices meet common anti-aging agent RD national standard.
Claims (3)
- A kind of 1. processing method of waste residue in high content age resistor TMQ production processes, it is characterized in that comprising the following steps：(1) by residue and aniline recovery, recovery acetone, 2,2,4- trimethyl -1,2- EEDQs monomers according to mass ratio 1: (0.1-0.5):(2-5):0.1 ratio is mixed in a kettle, 50-100 DEG C of reaction temperature, reaction time 1-3h；Instead Acetone is distilled to recover after should terminating；Reaction product is transferred to neutralization kettle；(2) configuration quality concentration 5-10% alkaline solutions；Neutralization kettle is added dropwise to, while defoamer is added dropwise；When pH value reaches 6-7 Stop being added dropwise；Water layer is separated after standing 30min；(3) oil phase enters monomer distillation kettle, 200-250 DEG C of vapo(u)rizing temperature；Stop distillation when in visor without backflow, cooling is granulated Finished product.
- 2. the method as described in claim 1, it is characterized in that described alkaline solution liquid is sodium hydroxide, potassium hydroxide.
- 3. the method as described in claim 1, it is characterized in that described defoamer is high-carbon alcohols, polyethers and organosilicon defoaming Agent.
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| 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 |
| 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 |
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)
| Title |
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| "我国橡胶助剂三废治理述评";肖军;《化学工业》;20110630;第29卷(第6期);第38－41页 * |
| "橡胶防老剂RD生产废水处理方法研究";苏宏 等;《烟台大学学报（自然科学与工程版）》;20030430;第16卷(第2期);第149－152页 * |
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