CN106188348A - A kind of utilization reclaims chlorinated rubber prepared by tire devulcanized rubber - Google Patents
A kind of utilization reclaims chlorinated rubber prepared by tire devulcanized rubber Download PDFInfo
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- CN106188348A CN106188348A CN201610572274.7A CN201610572274A CN106188348A CN 106188348 A CN106188348 A CN 106188348A CN 201610572274 A CN201610572274 A CN 201610572274A CN 106188348 A CN106188348 A CN 106188348A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
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Abstract
The invention discloses a kind of utilization and reclaim chlorinated rubber prepared by tire devulcanized rubber, its raw materials by weight portion meter includes: the hydrochloric acid solution of 10 15wt% 40 60 parts, recovery tire devulcanized rubber 8.0 15.0 parts, 3.0 9.0 parts of chlorine, dispersant 0.07 0.25 parts, emulsifying agent 0.07 0.15 parts and initiator 0.01 0.03 parts.Preparation method includes being mixed by raw material, being passed directly into liquid chlorine heating compressive reaction.It is that to be recycled rubber for tire be raw material to free of contamination Novel desulphurization technology that the present invention prepares the raw material that chlorinated rubber used, use the industrial products hydrochloric acid that aquo-acid phase chloridising prepares chlorinated rubber and containing hydrogen chloride 23 ~ 26wt%, the method overcomes Aqueous phase water consumption big, the problem higher containing sour cost of sewage disposal produced, high value added utilization for recycling round tire rubber opens new approach, with low cost.
Description
Technical field
The invention belongs to macromolecular material and modified field thereof, be more particularly to a kind of utilization and reclaim tire devulcanized rubber system
Standby chlorinated rubber.
Background technology
Chlorinated rubber (CR) is the chlorinated high polymers obtained after chlorination modified by natural rubber or synthetic rubber.Due to it
There is excellent film property, adhesiveness, corrosion resistance, anti-flammability and insulating properties, can be widely used for manufacturing easer, coating
With binding agent etc., it it is one of rising chloride fine chemical product.
The research early start of chlorinated rubber was in 1895, and first realized by present ICI company of Britain in 1917
Industrialized production.Chlorinated rubber, through the exploitation of more than 100 years and research, establishes perfect production and application system, a lot
The all a large amount of production and selling chlorinated rubber of enterprise.The traditional production method of chlorinated rubber has solid phase method, emulsion method, carbon tetrachloride molten
Agent method, wherein carbon tetrachloride solvent method is the main method producing chlorinated rubber the most both at home and abroad.According to " Montreal is discussed and decided
Book " regulation, developed country in close at the bottom of nineteen ninety-five with carbon tetrachloride produce chlorinated rubber device, use aqueous phase one after another
Method or other novel techniques.Asahi Electro-Chemical Co. Ltd of Japan uses water phase suspension to prepare the technology of chlorinated rubber, and builds up
800 t/a are without carbon tetrachloride method process units, and this technology products obtained therefrom is current state-of-the-art environmental type product.Germany
Bayer company then uses solvent exchange method, displaces carbon tetrachloride, reuses, the consumption of this new technique carbon tetrachloride
Measuring the lowest, be fully achieved the environmental requirement of Montreal protocol, the Cataldo company of Italy then uses liquid chlorine as chlorine
Agent and solvent, replace traditional carbon tetrachloride and prepare chlorinated rubber.
The production of China's chlorinated rubber starts from 20 century 70s, is first realized industrialization by Shanghai electrochemical factory, exists thereafter
The ground such as Guangzhou, Qingdao, Zhejiang, Jiangsu are constructed and put into operation in succession, but scale is all little, main employing carbon tetrachloride solvent method.From
Within 2005, rising, State Environmental Protection Administration specifies according to Montreal protocol, determines to stop and being limited in chlorinated rubber producing
Journey uses carbon tetrachloride, stopped using carbon tetrachloride completely by 2010.Relevant research unit of China and enterprise are from 20th century
Act the exploration research and development having begun to Aqueous phase manufacture chlorinated rubber the eighties, to replace carbon tetrachloride manufacture chlorinated rubber production work
Skill, the research and development of this technology are the most urgent.
Along with the development of auto industry and popularizing of private car, every annual meeting produces substantial amounts of waste tire, discarded wheel
Tire reclaims the utilization of rubber currently mainly Pintsch process, as fuel recovery, also has and waste tire reclaims rubber chunk
Rubber powder mixes Colophonium and carrys out laying road, and these recovery method surcharges are the lowest.Somebody takes turns with high temperature dynamic desulfurization technology handle
Tire recycles after reclaiming sizing material desulfurization, but high temperature desulfurizing is seriously polluted, and it is unpleasant to reclaim the sizing material stink obtained, it is impossible to push away
Wide application.
It is white outstanding it is proposed that directly and chlorine aqueous phase reactions prepares chlorinated rubber the butyl rubber raw material of Non-crosslinked
(CN201110201750, the preparation method of a kind of chlorinated scoline), but this method cannot directly allow and form three
The waste tire rubber chlorination of dimension macromolecular structure becomes chlorinated rubber.
The present inventor is it is proposed that one uses Aqueous phase technique, direct for the waste tire rubber through Vacuum Desulfurization before this
The patent (<a kind of chlorinated rubber, utilize and reclaim the method that tire devulcanized rubber prepares chlorinated rubber>of chlorinated rubber is prepared in chlorination
Number of patent application: ZL201410821944.5).Aqueous phase technique prepares chlorinated rubber technique more compared with traditional carbon tetrachloride method
Add environmental protection, there is certain competitiveness, but a large amount of low concentration of salt aqueous acid after preparing chlorinated rubber, can be produced.But it is near
Coming owing to environmental protection policy is increasingly tighter to wastewater from chemical industry discharge, Aqueous phase prepares the chlorinated rubber process cost containing acid sewage will
Rise, in some instances it may even be possible to have to stop producing.But, the recycling after waste tire desulfurization, especially high value added utilization
It is still that the important topic that people must solve.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that prepare the new method of chlorinated rubber, utilize and reclaim
Tire devulcanized rubber prepares the method for chlorinated rubber.Chlorinated rubber, to reclaim tire devulcanized rubber etc. as raw material, uses aquo-acid
Prepared by phase chloridising, preparation method is that waste tire resource high value added utilization opens frontier, contributes to solving discarded wheel
The environmental issue of tire comprehensive utilization, can improve the economic benefit reclaiming waste tire, reduces the cost of polymer composite；And
And preparation technology environment-friendly water-saving, easily implement, modified effect is good.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of utilization reclaims chlorinated rubber prepared by tire devulcanized rubber, and its raw materials by weight portion meter includes:
Hydrochloric acid solution 40-60 part of 10-15wt%, reclaim tire devulcanized rubber powder 8.0-15.0 part, chlorine 3.0-9.0 part, point
Powder 0.07-0.25 part, emulsifying agent 0.07-0.15 part and initiator 0.01-0.03 part.
Described recovery tire devulcanized rubber powder is through Vacuum Desulfurization work recycling round tire rubber (specification is TS-1)
Skill processes the rubber powder obtained.
Described emulsifying agent is one or both in tri-n-octyl methyl ammonium chloride and hexadecyltrimethylammonium chloride.
Described initiator is benzoyl peroxide or di-tert-butyl peroxide.
The preparation method of described dispersant is shown in the Chinese patent application of Application No. 201410821944.5.
The preparation method of chlorinated rubber as above, specifically includes following steps:
A, the hydrochloric acid solution being sequentially added into the 10-15wt% of formula ratio in reactor and recovery tire devulcanized rubber powder, stirring makes
Mix homogeneously；
B, the addition dispersant of formula ratio, emulsifying agent and initiator；
C, regulation are passed through the valve of liquid chlorine and are progressively passed through chlorine, heat up, before reactor temperature arrives steady temperature,
Control chlorine gas pressure, 0.35～0.50MPa, adds the chlorine of formula ratio 40-60%, is passed through remaining chlorine in the isothermal reaction stage
Gas, isothermal reaction stage control chlorine gas pressure is at 0.65～0.85 MPa；Described constant temperature is the temperature of 100-130 DEG C of any point；
After reaching the isothermal reaction stage, the continuation response time is 0.5-1.5h；Reaction is under agitation carried out；
After D, reaction terminate, after utilizing exhaust gas processing device to absorb the chlorine in reactor, product deacidification by centrifugation, reclaim 23 ~
The hydrochloric acid solution (can sell directly as technical hydrochloric acid product) of 26wt%；With deionized water, product is washed subsequently, and
Rear centrifuge dehydration, adds 23 ~ 26wt%'s of appropriate above-mentioned separation by gained water lotion (the low concentration acidic liquid after washing)
Hydrochloric acid solution, the hydrochloric acid solution making 10 ~ 15wt% returns chlorinating container recycling, the centrifugal solid content obtained as raw material
Through 45-60 DEG C of dry 2-4h, obtain powder chlorinated rubber product.
The present inventor, through improving with keen determination, has invented water system acid phase process new technology to prepare chlorinated rubber, has used concentration 10-
The aqueous hydrochloric acid solution of 15% is medium, is passed through liquid chlorine, through chlorination reaction, chlorinated rubber is prepared in discarded devulcanized rubber chlorination.This
Kind of technique has two big advantages, and one is the hydrochloric acid that waste acid water is concentration about 25% separating generation after chlorination, can be directly as work
Industry hydrochloric acid is sold.Prepare chlorinated rubber with Aqueous phase and will produce the waste water that low concentration is hydrochloric, and with the aquo-acid of the present invention
Phase method technique only needs to be washed with a small amount the chlorinated rubber being centrifugally separating to obtain, and it is above-mentioned that the washings of these Low acid mix part
Technique chlorizate filters the hydrochloric acid of obtained 25% and modulates 10-15% hydrochloric acid solution, again returns reactor as chlorination rubber
The feedstock circulation of glue uses, and whole technical process is not discharged acid-bearing wastewater, is greatly saved expenses of environmental protection；Two is the work of the present invention
Skill is except carrying out in addition in aqueous hydrochloric acid solution, and the pressure of reaction system increases, and chlorine is easier to penetrate into the molecule of rubber
Structure, the speed of rubber chlorination reaction is accelerated, hence it is evident that shortens the response time, is effectively improved the production efficiency of chlorinated rubber,
Waste tire devulcanized rubber becomes functional high molecule material, solves these key subjects of waste tire value added applications.
The beneficial effects of the present invention is:
(1) present invention prepares the raw material that chlorinated rubber used is that free of contamination Novel desulphurization technology is recycled rubber for tire and is
Raw material, uses aquo-acid phase chloridising to prepare chlorinated rubber, can need according to client, suitable adjusting process condition, adjust chlorine
Gas usage amount, can make the chlorinty of chlorinated rubber product change at 10%-35%, for the high value added utilization of recycling round tire rubber
Open new approach.The chlorinated rubber preparation method of the present invention does not produce acid-bearing wastewater simultaneously, and saving Aqueous phase technique needs
The expense of waste water process to be carried out, shortens synthesising reacting time, had both reduced energy consumption, and improve again production efficiency；
(2) present invention prepares raw material that chlorinated rubber used from waste tire, uses free of contamination Vacuum Desulfurization technology to enter
Row pretreatment, does not only pollute the environment, and low raw-material cost, prepare chlorinated rubber functional material from waste tire, can
To produce good economic benefit.The dispersant of present invention employing, emulsifying agent, with low cost, petrochemical materials can be reduced
Consumption, lignin Renewable resource, beneficially sustainable development can be made full use of.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Concretely comprising the following steps of preparation method:
In 100L titanium alloy stainless steel cauldron, it is sequentially added into dilute hydrochloric acid, recovery tire desulfurization process that concentration is 10-15wt%
Rubber powder afterwards, stirring is allowed to mix homogeneously；Add the dispersant of formula ratio, emulsifying agent and initiator；Regulation is passed through liquid
The valve of chlorine is progressively passed through liquid chlorine, heats up, and before reactor temperature arrives steady temperature, controls chlorine gas pressure and exists
0.35～0.50MPa, add the chlorine of formula ratio 40-60%, be passed through remaining chlorine, isothermal reaction stage in the isothermal reaction stage
Control chlorine gas pressure at 0.65～0.85 MPa；Described constant temperature is 100-130 DEG C of any point temperature；After reaching the isothermal reaction stage
The continuation response time is 0.5-1.5h；Reaction is under agitation carried out；After reaction terminates, exhaust gas processing device is utilized to absorb reactor
In chlorine after, product deacidification by centrifugation, reclaim 23 ~ 26wt% hydrochloric acid solution (can go out directly as technical hydrochloric acid product
Sell)；With deionized water, product is washed subsequently, then centrifuge dehydration, by (the low concentration acid after washing of gained water lotion
Property liquid) add the hydrochloric acid solution of 23 ~ 26wt% of appropriate above-mentioned separation, the hydrochloric acid solution making 10 ~ 15wt% returns as raw material
Returning chlorinating container recycling, the centrifugal solid content obtained, through 45-60 DEG C of dry 2-4h, obtains powder chlorinated rubber and produces
Product.
Raw material and instrument and equipment:
Reclaim tire and without the rubber powder (60 mesh, average 0.25mm) of desulfurization and reclaim tire Vacuum Desulfurization rubber powder (rule
Lattice are TS-1,60 mesh, average 0.25mm), Shanghai De Ban macromolecular material company limited provides；Chlorine, chemical industry is merged in Wuhu to be had
Limit company；The hydrochloric acid solution of 10-15wt% is the hydrochloric acid allotment of add deionized water and Wuhu Ronghui Chemical Co., Ltd. 35%
Prepare；Emulsifying agent: tri-n-octyl methyl ammonium chloride, hexadecyltrimethylammonium chloride, Xiamen Ying Ruowei Chemical Co., Ltd. product；
Initiator: benzoyl peroxide (Zouping, Shandong Heng Tai Chemical Co., Ltd.)；Di-tert-butyl peroxide DTBP(Dongying City Hai Jing
Chemical Co., Ltd.)；Dispersant uses the method described in the patent of invention that the present inventor had previously submitted to make by oneself.(< a kind of chlorination
Rubber, utilizes and reclaims the method that tire devulcanized rubber prepares chlorinated rubber > number of patent application: ZL201410821944.5).Natural
Rubber Thailand import RSS1 natural rubber, Shenyang Chun Enxianghua Products Co., Ltd buys, other raw materials and additive: for industry
Product, commercially available.Chlorinating container: Nanjing Bao Se limited company 100L titanium alloy stainless steel cauldron；Centrifuge, Zhejiang outstanding person's energy
Environmental protection scientific equipment company limited LWJ350 type centrifuge；Drying equipment: the SZG that Changzhou Ou Na drying equipment company limited produces
Type exsiccator.
In chlorinated rubber, chloride content determination measures rubber and rubber according to standard GB/T/T 9872-1998 oxygen flask combustion
Bromine and the content of chlorine in glue goods.
Embodiment 1:
In 100L titanium alloy stainless steel cauldron, being sequentially added into 50L concentration is that the dilute hydrochloric acid of 13wt%, 12Kg reclaim tire desulfurization
Rubber powder after process, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.090Kg, emulsifying agent three
Octylmethylammonium chloride 0.08Kg, initiator B PO(dibenzoyl peroxide) 0.015Kg, agitating heating 0.5h, reach in temperature
Start to be passed through the chlorine of 0.40 MPa when 80 DEG C, control be passed through the tolerance of chlorine and be progressively warming up to 115 DEG C and keep constant temperature,
It is 2.4Kg that early stage leads to chlorine dose, and it is 3.5Kg that the constant temperature stage leads to chlorine dose, and it is 0.70 MPa that the constant temperature stage leads to chlorine gas pressure, the constant temperature stage
The logical chlorine time is 0.5 h；Being passed through after chlorine process terminates, keep temperature to continue reaction 0.8h, reaction terminates；Utilize tail gas
After processing means absorbs the chlorine in reactor, product deacidification by centrifugation, obtain 42 L acid solution, acid solution measures and contains containing HCl
Amount 25wt%, solid content washes with water twice with 5L deionization respectively, obtains 3.6wt% dilute hydrochloric acid 9.7 L, and solid content is through 50 DEG C
Being dried 4h, obtain 16.7Kg chlorinated rubber powder, recording chlorinity is 32.8 %.
Embodiment 2:
In 100L titanium alloy stainless steel cauldron, being sequentially added into 55L concentration is that the dilute hydrochloric acid of 11wt%, 14Kg reclaim tire desulfurization
Rubber powder after process, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.085Kg, emulsifying agent ten
Six alkyl trimethyl ammonium chloride 0.08Kg, initiator di-tert-butyl peroxide DTBP 0.015Kg, agitating heating 0.5h, in temperature
Degree reaches to start when 85 DEG C to be passed through the chlorine of 0.45 MPa, controls be passed through the tolerance of chlorine and be progressively warming up to 115 DEG C and keep
Constant temperature, it is 3.0Kg that early stage leads to chlorine dose, and it is 3.9Kg that the constant temperature stage leads to chlorine dose, and it is 0.75 MPa that the constant temperature stage leads to chlorine gas pressure, permanent
It is 0.5 h that thermophase leads to the chlorine time；Being passed through after chlorine process terminates, keep temperature to continue reaction 1.0 h, reaction terminates；
After utilizing exhaust gas processing device to absorb the chlorine in reactor, product, through washing, centrifugal deacidification, obtains 45 L acid solution, acid
Liquid measures the content 26wt% Han HCl, and solid content washes with water twice with 5L deionization respectively, obtains 3.7wt% dilute hydrochloric acid 9.7 L, Gu
Shape thing, through 50 DEG C of dry 4h, obtains 18.7Kg chlorinated rubber powder, and recording chlorinity is 31.7 %.
Embodiment 3:
In 100L titanium alloy stainless steel cauldron, being sequentially added into 55L concentration is that the dilute hydrochloric acid of 14wt%, 15Kg reclaim tire desulfurization
Rubber powder after process, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.090Kg, emulsifying agent three
Octylmethylammonium chloride 0.08Kg, initiator (BPO, dibenzoyl peroxide) 0.015Kg, agitating heating 0.5h, reach in temperature
Start to be passed through the chlorine of 0.40 MPa during to 85 DEG C, control be passed through the tolerance of chlorine and be progressively warming up to 110 DEG C and keep permanent
Temperature, it is 2.9Kg that early stage leads to chlorine dose, and it is 3.2Kg that the constant temperature stage leads to chlorine dose, and it is 0.55 MPa that the constant temperature stage leads to chlorine gas pressure, constant temperature
It is 0.5 h that stage leads to the chlorine time；Being passed through after chlorine process terminates, keep temperature to continue reaction 1.0h, reaction terminates；Utilize
After exhaust gas processing device absorbs the chlorine in reactor, product deacidification by centrifugation, obtain 44 L acid solution, acid solution measures and contains
HCl content 25wt%, solid content washes with water twice with 5L deionization respectively, obtains 3.6wt% dilute hydrochloric acid 9.6 L, solid content warp
Crossing 50 DEG C of dry 4h, obtain 19.7Kg chlorinated rubber powder, recording chlorinity is 31.8 %.
Embodiment 4:
In 100L titanium alloy stainless steel cauldron, being sequentially added into 50L concentration is that the dilute hydrochloric acid of 12wt%, 13Kg reclaim tire desulfurization
Rubber powder after process, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.09Kg, emulsifying agent three
Octylmethylammonium chloride 0.08Kg, initiator initiator di-tert-butyl peroxide DTBP0.015Kg, agitating heating 0.5h,
Temperature reaches to start when 85 DEG C to be passed through the chlorine of 0.40 MPa, controls be passed through the tolerance of chlorine and be progressively warming up to 105 DEG C and protect
Holding constant temperature, it is 1.5Kg that early stage leads to chlorine dose, and it is 2.0 Kg that the constant temperature stage leads to chlorine dose, and it is 0.40 MPa that temperature section leads to chlorine soil fertility, constant temperature
It is 0.5 h that stage leads to the chlorine time；Being passed through after chlorine process terminates, keep temperature to continue reaction 0.8h, reaction terminates；Utilize
After exhaust gas processing device absorbs the chlorine in reactor, product, through washing, centrifugal deacidification, obtains 41 L acid solution, and acid solution is surveyed
Surely the content 23wt% Han HCl, solid content washes with water twice with 5L deionization respectively, obtains 3.6wt% dilute hydrochloric acid 9.7 L, solid content
Through 50 DEG C of dry 4h, obtaining 15.3Kg chlorinated rubber powder, recording chlorinity is 20.8 %.
Embodiment 5:
In 100L titanium alloy stainless steel cauldron, being sequentially added into 55L concentration is that the dilute hydrochloric acid of 14wt%, 13Kg reclaim tire desulfurization
Rubber powder after process, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.090Kg, emulsifying agent ten
Six alkyl trimethyl ammonium chloride 0.04Kg and the mixture of tri-n-octyl methyl ammonium chloride 0.04Kg, initiator (BPO, peroxidating two
Benzoyl) 0.015Kg, agitating heating 0.5h, start to be passed through the chlorine of 0.40 MPa when temperature reaches 85 DEG C, control to be passed through
The tolerance of chlorine is also progressively warming up to 105 DEG C and keeps constant temperature, and it is 2.5Kg that early stage leads to chlorine dose, and the constant temperature stage leads to chlorine dose and is
3.2Kg, it is 0.60 MPa that the constant temperature stage leads to chlorine gas pressure, and it is 0.5 h that the constant temperature stage leads to the chlorine time；It is passed through chlorine process to terminate
Afterwards, keeping temperature to continue reaction 1.0h, reaction terminates；After utilizing exhaust gas processing device to absorb the chlorine in reactor, product
Deacidification by centrifugation, obtains 42 L acid solution, and acid solution measures the content 23wt% Han HCl, and solid content washes with water with 5L deionization respectively
Twice, obtaining 3.9wt% dilute hydrochloric acid 9.6 L, solid content, through 50 DEG C of dry 4h, obtains 17.7Kg chlorinated rubber powder, records
Chlorinity is 30.8 %.
Comparative example 1: prepare chlorinated rubber with the waste tire rubber powder processed without Vacuum Desulfurization
In 100L titanium alloy stainless steel cauldron, be sequentially added into 50L concentration be the dilute hydrochloric acid of 13wt%, 12Kg reclaim tire without
The rubber powder that Vacuum Desulfurization processes, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant 0.090Kg, emulsifying
Agent tri-n-octyl methyl ammonium chloride 0.08Kg, initiator (BPO, dibenzoyl peroxide) 0.015Kg, agitating heating 0.5h, in temperature
Degree reaches to start when 80 DEG C to be passed through the chlorine of 0.40 MPa, controls be passed through the tolerance of chlorine and be progressively warming up to 115 DEG C and keep
Constant temperature, it is 2.4Kg that early stage leads to chlorine dose, and it is 3.5Kg that the constant temperature stage leads to chlorine dose, and it is 0.70 MPa that the constant temperature stage leads to chlorine gas pressure, permanent
It is 0.5 h that thermophase leads to the chlorine time；Being passed through after chlorine process terminates, keep temperature to continue reaction 0.8h, reaction terminates；Profit
After absorbing the chlorine in reactor with exhaust gas processing device, product, through washing product deacidification by centrifugation, obtains 42 L acid solution,
Acid solution measures the content 31wt% Han HCI, and solid content washes with water twice with 5L deionization respectively, obtains 4.6wt% dilute hydrochloric acid 9.7
L, solid content, through 50 DEG C of dry 4h, obtains 12.7Kg chlorinated rubber powder, and recording chlorinity is 5.8 %.
Comparative example 2: be that chlorinated rubber prepared by raw material with natural rubber
In 100L titanium alloy stainless steel cauldron, being sequentially added into 50L concentration is the dilute hydrochloric acid of 13wt%, the sky of 12Kg Thailand import
The rubber powder (60 mesh, average 0.25mm) that so rubber is worn into, stirring is allowed to mix homogeneously；It is sequentially added into lignin derivative dispersant
0.090Kg, emulsifying agent tri-n-octyl methyl ammonium chloride 0.08Kg, initiator (BPO, dibenzoyl peroxide) 0.015Kg, stirring adds
Hot 0.5h, starts to be passed through the chlorine of 0.40 MPa when temperature reaches 80 DEG C, controls be passed through the tolerance of chlorine and be progressively warming up to
115 DEG C and keep constant temperature, it is 2.4Kg that early stage leads to chlorine dose, and it is 3.5Kg that the constant temperature stage leads to chlorine dose, and the constant temperature stage leads to chlorine gas pressure and is
0.70 MPa, it is 0.5 h that the constant temperature stage leads to the chlorine time；It is passed through after chlorine process terminates, keeps temperature to continue reaction 0.8h,
Reaction terminates；After utilizing exhaust gas processing device to absorb the chlorine in reactor, product, through washing, centrifugal deacidification, obtains 42 L acid
Property solution, measure HCI content 25wt% in acid solution, solid content washes with water twice with 5L deionization respectively, obtains the dilute salt of 3.6wt%
Acid 9.7 L, solid content, through 50 DEG C of dry 4h, obtains 16.5Kg chlorinated rubber powder, and recording chlorinity is 32.3 %.
Comparative example 3: use Aqueous phase technique, prepare chlorinated rubber with waste tire devulcanized rubber for raw material
In 100L titanium alloy stainless steel cauldron, it is sequentially added into 60 L deionized waters, Lignin Dispersants 0.075Kg, emulsifying agent
Tri-n-octyl methyl ammonium chloride 0.08Kg, initiator B PO(dibenzoyl peroxide) 0.015Kg, waste tire devulcanized rubber powder 2.0
Kg, agitating heating 0.5h, start to be passed through the chlorine of 0.28 MPa when temperature reaches 80 DEG C, control to be passed through the tolerance of chlorine also
Progressively being warming up to 115 DEG C and keep constant temperature, it is 0.5Kg that early stage leads to chlorine dose, and it is 0.7Kg that the constant temperature stage leads to chlorine dose, the constant temperature stage leads to
Chlorine gas pressure is 0.30MPa, and it is 0.5h that the constant temperature stage leads to the chlorine time；It is passed through after chlorine process terminates, keeps temperature to continue
Reaction 1.0h, reaction terminates.After utilizing exhaust gas processing device to absorb the chlorine in reactor, product, through washing, centrifugal deacidification, produces
Raw acid-bearing wastewater 53 L containing 4%HCI, with in the sodium carbonate liquor that 5.5L molar concentration is 1Mol/L and rear centrifuge dehydration, produces
Raw waste water 5.4 L, then clean centrifugal with deionized water 5L, producing waste water 4.9L, solid content, through 55 DEG C of dry 3.5h, obtains
2.81Kg chlorinated rubber powder, recording chlorinity is 30.3%.
Chlorinated rubber yield obtained by embodiment 1-5 and comparative example 1,2,3, chlorinity and generation waste water weight are shown in Table
1:
The yield of table 1 chlorinated rubber, chlorinty and generation waste water weight thereof
Embodiment 1-5 show that the water system acid phase process that the present invention proposes utilizes waste tire devulcanized rubber to prepare chlorinated rubber, can
Preparing the chlorinated rubber that chlorinty is different adjusting chlorine intake as required, this method does not produce acid waste water, energy-conservation
Environmental protection has the value of popularization and application.
But, comparative example 1 uses the waste tire powder processed without desulfurization, by same chlorination reaction condition, due to
Three-dimensional cross-linked macromolecular structure, even if carrying out chlorination reaction in hydrochloric acid solution, chlorine molecule is also relatively difficult to penetrate into inside
There is chlorination reaction, so chlorinty is relatively low in the product obtained；And being difficult to without the tire powder of desulfurization, even if chlorine
Change modification also cannot effectively utilize.
The result of comparative example 2 shows that with natural rubber be raw material, and the acid phase process using this patent to propose can also manufacture chlorine
The chlorinated rubber of content about 30%, but due to reasons such as geography, weathers, the natural rubber majority of China leans on import, and price is held high
, the cost of waste tire devulcanized rubber only has the four of natural rubber, and 1/5th.The present invention is not only the most sharp waste tire
With, and considerable economic benefit can be produced.
Comparative example 3 for I before this patent of invention (< a kind of chlorinated rubber utilizes and reclaims tire devulcanized rubber and prepare chlorination
The method of rubber > number of patent application: ZL201410821944.5) chlorination that uses, although also can obtain chlorinty 30% left
Right chlorinated rubber, but produce a large amount of acid-bearing wastewater, and it is a great difficult problem that waste water processes.Acid phase process not only preparation process contracts
Subtracting reduction energy consumption, most important innovation is that the acid phase process water consumption of the present invention is few, overcomes Aqueous phase and prepares chlorinated rubber and produced
The problem of raw a large amount of sour waters.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (5)
1. one kind utilizes chlorinated rubber prepared by recovery tire devulcanized rubber, it is characterised in that: its raw materials by weight portion meter bag
Include:
Hydrochloric acid solution 40.0-60.0 part of 10-15wt%,
Reclaim tire devulcanized rubber powder 8.0-15.0 part,
Chlorine 3.0-9.0 part,
Dispersant 0.07-0.25 part,
Emulsifying agent 0.07-0.15 part,
Initiator 0.01-0.03 part.
The most according to claim 1 utilization reclaims chlorinated rubber prepared by tire devulcanized rubber, it is characterised in that: described
Reclaiming tire devulcanized rubber powder is the rubber powder that recycling round tire rubber is obtained through Vacuum Desulfurization PROCESS FOR TREATMENT.
The most according to claim 1 utilization reclaims chlorinated rubber prepared by tire devulcanized rubber, it is characterised in that: described breast
Agent is one or both in tri-n-octyl methyl ammonium chloride and hexadecyltrimethylammonium chloride.
The most according to claim 1 utilization reclaims chlorinated rubber prepared by tire devulcanized rubber, it is characterised in that draw described in:
Sending out agent is benzoyl peroxide or di-tert-butyl peroxide.
5. the method for the chlorinated rubber prepared as described in claim 1-4, it is characterised in that: specifically include following steps:
A, the hydrochloric acid solution being sequentially added into the 10-15wt% of formula ratio in reactor and recovery tire devulcanized rubber powder, stirring
It is allowed to mix homogeneously；
B, the addition dispersant of formula ratio, emulsifying agent and initiator；
C, regulation are passed through the valve of liquid chlorine and are progressively passed through chlorine, heat up, before reactor temperature arrives steady temperature,
Control chlorine gas pressure, 0.35～0.50MPa, adds the chlorine of formula ratio 40-60%, is passed through remaining chlorine in the isothermal reaction stage
Gas, isothermal reaction stage control chlorine gas pressure is at 0.65～0.85 MPa；Described constant temperature is 100-130 DEG C of any point temperature；Reach
After the isothermal reaction stage, the continuation response time is 0.5-1.5h；Reaction is under agitation carried out；
After D, reaction terminate, after utilizing exhaust gas processing device to absorb the chlorine in reactor, product deacidification by centrifugation, reclaim 23 ~
The hydrochloric acid solution of 26wt%；With deionized water, product is washed subsequently, then centrifuge dehydration, gained water lotion is added suitable
Measuring the hydrochloric acid solution of 23 ~ 26wt% of above-mentioned separation, the hydrochloric acid solution making 10 ~ 15wt% returns chlorinating container again as raw material
Utilizing, the centrifugal solid content obtained, through 45-60 DEG C of dry 2-4h, obtains powder chlorinated rubber product.
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Cited By (1)
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| CN108102011A (en) * | 2018-02-28 | 2018-06-01 | 中国天辰工程有限公司 | A kind of aftertreatment technology and device of high polymer chlorination reaction |
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| CN108102011A (en) * | 2018-02-28 | 2018-06-01 | 中国天辰工程有限公司 | A kind of aftertreatment technology and device of high polymer chlorination reaction |
| CN108102011B (en) * | 2018-02-28 | 2021-04-02 | 中国天辰工程有限公司 | Post-treatment process and device for high polymer chlorination reaction |
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