WO2019090938A1 - 一种多阶螺杆连续脱硫制备再生橡胶的方法 - Google Patents

一种多阶螺杆连续脱硫制备再生橡胶的方法 Download PDF

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Publication number
WO2019090938A1
WO2019090938A1 PCT/CN2017/118796 CN2017118796W WO2019090938A1 WO 2019090938 A1 WO2019090938 A1 WO 2019090938A1 CN 2017118796 W CN2017118796 W CN 2017118796W WO 2019090938 A1 WO2019090938 A1 WO 2019090938A1
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Prior art keywords
rubber powder
screw extruder
desulfurization
temperature
section
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PCT/CN2017/118796
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English (en)
French (fr)
Inventor
张立群
任冬云
史金炜
戈风行
陈成杰
汪冯新
王杰
张植俞
陆涛
刘晓博
杨晓彤
Original Assignee
北京化工大学
南京绿金人橡塑高科有限公司
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Application filed by 北京化工大学, 南京绿金人橡塑高科有限公司 filed Critical 北京化工大学
Priority to EP17931711.0A priority Critical patent/EP3611221B8/en
Priority to US16/476,535 priority patent/US11453758B2/en
Publication of WO2019090938A1 publication Critical patent/WO2019090938A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
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    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
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    • B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
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    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/277—Recovery or reuse of energy or materials of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2888—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules in band or in strip form, e.g. rubber strips
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    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Definitions

  • the invention relates to a new method for preparing reclaimed rubber, in particular to a method for regenerating waste rubber by a multi-stage screw extruder, and belongs to the field of waste rubber recycling.
  • the raw rubber is crosslinked by a linear polymer chain to form a three-dimensional network structure, so that the rubber has high strength, high elasticity, high wear resistance and corrosion resistance. Meet the needs of production and life.
  • Sulfur vulcanization system is one of the most commonly used methods for rubber vulcanization.
  • the S-S bond and C-S bond are used to connect the polymer chain to form a crosslinked network.
  • After the service life of the thermosetting vulcanized rubber product with three-dimensional network structure is insoluble and infutable, it is difficult to be treated, and it becomes one of the most harmful wastes in industrial hazardous waste.
  • the global production of waste tires reached 40.47 million tons.
  • the preparation of reclaimed rubber can achieve the purpose of recycling rubber. It has received extensive attention and is the most important recycling method of China's waste rubber. The annual output exceeds 4.5 million tons, accounting for 80% of the global recycled rubber production.
  • the bond energy difference of the chemical bond is that the bond energy of the C-C bond is larger than the bond energy of the C-S bond and the S-S bond, and the C-S bond and the S-S bond are broken by controlling the application of heat without breaking the main chain.
  • the difference in the elastic coefficient of the chemical bond means that the C-C bond, the C-S bond, and the S-S bond are selectively cleaved by the shear coefficient under the action of shearing.
  • the S-S bond is selectively interrupted by the bond energy of the chemical bond, and has been widely used in China, forming a desulfurization regeneration process mainly based on "high temperature and high pressure dynamic desulfurization".
  • the regenerant and water are added together into the desulfurization tank, the working pressure is about 2.2 MPa, the working temperature is about 220 ° C, the desulfurization time is about 3 hours, and the desulfurization rubber powder is obtained by pressure relief.
  • the activator penetrates into the interior of the waste rubber and reacts with it, destroying the crosslinked network, making it quasi-linear and reprocessable.
  • thermochemical, strong shear composite desulfurization equipment and its desulfurization method adjust the threaded components by adding pins on the single-screw barrel, so that the single screw has the function of maintaining the thermochemical reaction.
  • High-shearing of the desulfurized material to enhance the desulfurization effect of the thermochemical reaction The material is not always in a compact state in a single screw, and oxygen is inevitably mixed. The degradation of the rubber main chain is severe under high temperature conditions.
  • Zhang Liqun et al (CN102977404B, a method for continuously preparing reclaimed rubber in a double-stage twin-screw extruder), etc., after pretreatment of the waste rubber powder and the regenerant in a mixer, the sample is allowed to stand at a high temperature to allow the regenerant to fully penetrate the swollen rubber powder. Then add the counter-rotating twin-screw extruder to replace the traditional high-temperature and high-pressure dynamic reaction tank. The desulfurized rubber powder enters the co-rotating twin-screw extruder and applies high shear at low temperature to replace the refiner. The viscosity of the regenerant is still very high at 50 °C ⁇ 100 °C.
  • Ni Xuewen et al. (CN102888030B waste rubber high temperature and atmospheric pressure regeneration process) does not add any softener and catalyst.
  • the rubber powder is directly stirred and forced into a twin-screw extruder through a forced feeding device to apply high temperature and high shear to achieve rapid desulfurization reaction.
  • the cooled material is added to the variable frequency open type rubber mixer for rapid shearing, and then refined in an open type rubber mixer, and finally filtered through a rubber gel.
  • the waste rubber powder without adding any additives has high viscosity and high hardness.
  • the temperature of the twin-screw heating softening zone is as high as 300-350 °C to soften the rubber powder, which inevitably leads to degradation of the main chain and causes the mechanical properties of the reclaimed rubber to decrease. .
  • CN104004222B a waste rubber low-temperature continuous regeneration device and process method
  • using a mixer to pre-mix and disassemble the waste rubber powder and the regenerant, and then adding a twin-screw extruder to carry out a mechanochemical reaction and adding it through a conveyor belt.
  • Refining is carried out on an open mill, and after refining, reclaimed rubber is obtained.
  • Open conveyors and refining equipment pollute the environment; materials produced intermittently from the mixer are discharged directly from the discharge port to the inlet of the twin-screw extruder, resulting in unstable production processes.
  • Desulfurization can be selectively broken by controlling the appropriate shear by the difference in the elastic modulus of the chemical bond, and there is no problem of the "core-shell" structure due to uneven permeation.
  • the object of the present invention is to overcome the deficiencies of the prior art utilizing the bond energy difference of a chemical bond or the elastic coefficient difference of a chemical bond, and to provide a method for continuously preparing a reclaimed rubber, which is prepared by continuously desulfurizing a multi-stage screw.
  • the invention is realized by the following process: a method for preparing a reclaimed rubber by continuous desulfurization of a multi-stage screw, characterized in that the method comprises the penetration of a regenerant and the preliminary desulfurization, desulfurization process and refining process of the waste rubber powder,
  • the waste rubber powder and softener are treated in a mixer at 60 ° C ⁇ 120 ° C for 5 min ⁇ 25 min, then into the 60 ° C ⁇ 120 ° C insulation buffer tank, through a continuous closed heat transfer metering device into a counter-rotating twin-screw In the machine, stay at 100 ° C ⁇ 340 ° C for 1 min ⁇ 6min to complete the uniform penetration of the softener into the rubber powder and the preliminary desulfurization of the waste rubber powder, and then cooled to 40 ° C ⁇ 80 ° C under a closed condition by a continuous cooling device,
  • the initial desulfurization material with Mooney viscosity of 100-230 is then continuously conveyed to the
  • the temperature of the mandrel is between 20 ° C and 110 ° C, and the desulfurization reaction is completed in 1 min to 6 min.
  • the Mooney viscosity is 70-150 desulfurized rubber powder extruded by the extruder, and cooled to 25 ° C under a closed condition by a continuous cooling device.
  • the mass ratio of waste rubber powder to softener and activator is 100: (2 ⁇ 20): (0.01 ⁇ 3);
  • Preferred softeners are a mixture of one or more of coal tar, aromatic oil, pine tar, tall oil, naphthenic oil, dipentene, paraffin oil, oleic acid, cottonseed oil, rosin, and the activator is aromatic hydrocarbon two. a mixture of one or more of a sulfide, a polyalkylphenol sulfide, a phenylthiol, an amine compound.
  • the waste rubber powder used is one or a mixture of waste radial tire rubber powder or waste car tire rubber powder.
  • the multi-screw extruder used is one of a co-rotating twin-screw extruder or a co-rotating parallel three-screw extruder.
  • the preferred counter-rotating twin-screw extruder has a heating exhaust section temperature of 120 ° C to 200 ° C, a holding section temperature of 200 ° C to 340 ° C, and a cooling section temperature of 100 ° C to 200 ° C.
  • the barrel temperature of the mixing section of the second multi-screw extruder is between 40 ° C and 70 ° C
  • the barrel temperature of the shear section is between 70 ° C and 90 ° C
  • the barrel temperature of the cooling section is between 30 ° C and 60 ° C.
  • the barrel temperature of the first material conveying section of the third multi-screw extruder is between 0 ° C and 25 ° C
  • the barrel temperature of the pre-shearing section is between 5 ° C and 40 ° C
  • the barrel temperature of the second material conveying section At 5 ° C ⁇ 25 ° C
  • the barrel temperature of the second shear section is -5 ° C ⁇ 35 ° C
  • the barrel temperature of the third material conveying section is 0 ° C ⁇ 45 ° C.
  • the invention rationally designs the permeation of the softener and the preliminary desulfurization, desulfurization process and refining process of the waste rubber powder, and adopts the screw extruder in series as the desulfurization regeneration production equipment of the waste rubber powder, thereby ensuring the safe and continuous process of the waste rubber regeneration process. Production. After the softener and the waste rubber powder are initially mixed, the uniform penetration of the softener is realized in the anisotropic twin screw. Due to the lack of the activator, the molecular chain breaks less, and the rubber powder particles are basically in the initial desulfurization state of uniform swelling, which is large.
  • the molecular chain is in an extended state; the oxygen is added to the second multi-screw extruder, and the activator is uniformly dispersed in the mixing section by the good compatibility of the activator and the softener, and the activator activity is higher in the shearing zone temperature.
  • Large, desulfurization regeneration is achieved by activator and shearing action, and desulfurized rubber powder with uniform desulfurization is obtained after cooling; the structure of the rubber powder undergoes desulfurization changes obviously, and it is selected to be refined under low temperature conditions in the third multi-screw extruder. It avoids the breakage of the macromolecular backbone and effectively reduces the Mooney viscosity of the desulfurized rubber powder and improves the processing performance.
  • the softener and the activator are sequentially added at different positions, thereby avoiding the uneven desulfurization caused by the reaction of the inner side of the waste rubber powder when the activator and the softener are simultaneously added; the fully swollen rubber powder obtained by the uniform penetration of the softener
  • the molecular chain of the particles is in an extended state, which greatly reduces the temperature required for desulfurization, selectively interrupts the SS bond under the dual action of activator and shearing force, greatly improves the desulfurization efficiency while ensuring the mechanical properties;
  • hard particle desulfurized rubber powder can quickly reduce Mooney viscosity and reduce energy consumption during refining.
  • the counter-rotating twin-screw extruder has strong positive displacement conveying ability, can reasonably adjust the penetration time, and has self-cleaning ability to avoid process changes caused by carbonization and scaling after long-term use, stable product quality and convenient maintenance;
  • the design of the threaded components makes multiple changes in the flow direction and flow rate.
  • a multi-screw extruder that meets the requirements of both desulfurization and refining is designed to achieve sealing, continuous and automation.
  • the rationally designed device overcomes the defects of the previous desulfurization regeneration method and greatly reduces the energy consumption.
  • the entire preparation process is completed under closed oxygen barrier conditions, and the obtained reclaimed rubber has excellent performance, and is safe, simple, continuous and energy-saving.
  • Figure 1 is a schematic view of the system
  • FIG. 1 Schematic diagram of the counter-rotating twin-screw extruder
  • Figure 3 is a schematic diagram of the same direction parallel three-screw
  • Figure 4 is the same direction twin screw
  • the preliminary desulfurization rubber powder of 195 was cooled to 50 °C by a cooling conveyor, then docked into a second co-rotating twin-screw extruder, and 0.1 part of activator 2, 2'-disulfide double (6- was added from the side feed.
  • activator 2 2'-disulfide double (6- was added from the side feed.
  • Tert-butyl-p-phenol the barrel temperature of the mixing section is 45 °C
  • the barrel temperature of the shearing section is 70 °C
  • the barrel temperature of the cooling section is 35 °C
  • the shearing action in the extruder is 3 min.
  • the desulfurization rubber powder having the Mooney viscosity of 110 is obtained, and is added to the third co-parallel three-screw extruder through the closed connection cooling device, and the barrel temperature of the first material conveying section is 15 ° C, and the pre-shear section
  • the barrel temperature is 30 ° C
  • the barrel temperature of the second material conveying section is 20 ° C.
  • the barrel temperature of the second shearing section is 25 ° C
  • the barrel temperature of the third material conveying section is 15 ° C
  • the mandrel temperature is 10 ° C
  • the shearing effect in the extruder is 3 min after being extruded by the machine head.
  • the material was cooled to 40 ° C by means of a molding device and a cooling device to obtain a reclaimed rubber product having a Mooney viscosity of 53.
  • the preliminary desulfurization rubber powder of 180 is cooled to 60 ° C by a cooling conveyor, then butted into a second co-rotating twin-screw extruder, and 3.0 parts of activator diphenyl disulfide is added from the side feed, and the mixing section is machine
  • the cylinder temperature is 55 °C
  • the barrel temperature of the shearing section is 80 °C
  • the barrel temperature of the cooling section is 40 °C
  • the shearing effect in the extruder is 3 min.
  • the rubber powder is added to the third co-parallel three-screw extruder through a closed connection cooling device.
  • the barrel temperature of the first material conveying section is 15 ° C, and the barrel temperature of the pre-shearing section is 30 ° C, the second material.
  • the barrel temperature of the conveying section is 20 ° C, and the barrel temperature of the second cutting section
  • the degree is 25 ° C
  • the barrel temperature of the third material conveying section is 15 ° C
  • the mandrel temperature is 10 ° C
  • the shearing effect in the extruder is 3 min.
  • Example 3 100 parts of waste tire radial tire tread rubber powder was added, 8 parts of tall oil, 6 parts of pine tar and 4 parts of rosin were added as softener, and the rubber powder and softener were mixed and stirred at 100 ° C for 20 min in a blender. After that, it is added to the first counter-rotating twin-screw extruder through a continuous sealed heat-conveying metering device, and the temperature is set to 160 ° C for the heating exhaust section, 260 ° C for the reaction section, 140 ° C for the cooling section, and the material is retained for 4 minutes.
  • a preliminary desulfurization rubber powder with a Mooney viscosity of 160 was obtained, cooled to 55 ° C by a cooling conveyor, and then butted into a second co-rotating twin-screw extruder, and 0.2 part of the activator was added from the side feed.
  • the temperature of the barrel of the amine and mixing section is 65 °C
  • the barrel temperature of the shearing section is 90 °C
  • the barrel temperature of the cooling section is 50 °C
  • the shearing effect in the extruder is 3 min after being extruded by the machine head.
  • the Mooney viscosity 90 desulfurization rubber powder is then butted into the third co-parallel three-screw extruder.
  • the barrel temperature of the first material conveying section is 5 ° C
  • the cylinder temperature of the pre-shear section is 15 ° C.
  • the barrel temperature of the second material conveying section is 10 ° C
  • the barrel temperature of the second cutting section For 20 ° C, the barrel temperature of the third material conveying section is 15 ° C
  • the mandrel temperature is 15 ° C
  • the shearing effect in the extruder is 2 min after being extruded by the machine head, and the material is cooled by the molding device and the cooling device.
  • a Regeneration Glue product with a Mooney viscosity of 50 was obtained.

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Abstract

一种多阶螺杆连续脱硫制备再生橡胶的方法，属废旧橡胶循环再利用领域。初步混合的胶粉和软化剂经连续密闭保温输送计量装置（1），压实加入第一台异向双螺杆挤出机，在挤出机内温度的作用下软化剂均匀渗透废胶粉，废胶粉初步脱硫；经输送装置冷却后，对接进入第二台多螺杆挤出机内，通过活化剂和剪切作用实现快速脱硫再生；制备的脱硫胶粉经冷却输送装置（6），进入第三台串联的多螺杆挤出机内，在低温下通过剪切作用改善加工性能，挤出后通过成型装置和冷却装置，最终包装得到再生橡胶。整个流程在密闭隔氧条件下完成，实现了安全、简单、连续的脱硫再生，具有节能、环保的优点，所得再生胶性能优异。

Description

一种多阶螺杆连续脱硫制备再生橡胶的方法 技术领域
本发明涉及一种制备再生胶的新方法，尤其涉及多阶螺杆挤出机再生废橡胶的方法，属于废旧橡胶循环再利用领域。
背景技术
为了改善生胶的性能，需要对生胶进行硫化加工，生胶由线性高分子链交联形成三维网状结构，从而使胶料具备高强度、高弹性、高耐磨、抗腐蚀等特点，满足生产生活的需要。硫黄硫化体系是橡胶硫化最常用的方法之一，通过S-S键、C-S键连接高分子链形成交联网络。具有三维网状结构的热固性硫化橡胶制品达到使用寿命后，不溶不熔，难以进行处理，成为工业有害废弃物中危害最大的垃圾之一，2015年全球产生废轮胎高达4047万吨。制备再生胶可以达到循环利用橡胶的目的，受到广泛的重视，是中国废橡胶的最主要再利用方式，年产量超过450万吨，约占全球再生橡胶产量的80％。
目前，国际上关于废橡胶的断键再生机理主要有两种观点：1.化学键的键能差；2.化学键的弹性系数差。所谓化学键的键能差就是利用C-C键的键能大于C-S键和S-S键的键能，通过控制施加热的所用，使C-S键和S-S键断裂，而不使主链断裂。化学键的弹性系数差是指C-C键、C-S键、S-S键三者在剪切的作用下，利用弹性系数的不同，选择性断裂交联键。
通过化学键的键能差选择性的打断S-S键，在中国得到了广泛的应用，形成了以“高温高压动态脱硫”为主的脱硫再生工艺。将再生剂和水一起加入脱硫罐中，工作压力2.2MPa左右，工作温度约220℃，脱硫时间3小时左右，泄压得到脱硫胶粉。活化剂在软化剂的辅助下，渗透并进入废橡胶内部与之发生反应，破坏交联网络，使之准线性化、可再加工。但是高温条件下再生剂由外向内边渗透边反应的过程中，容易引起废胶粉内外脱硫程度不均匀，产生“核—壳”结构；同时搅拌转速慢，脱硫不均匀。为了避免胶粉表面过度脱硫引起力学性能的下降，脱硫胶粉的门尼粘度往往比较高，脱硫程度较低，需经3～4台高速精炼机多次过辊压炼，才能制备加工性能良好的再生胶。长时间的高温高压存在严重的安全隐患，间歇操作生产率低，罐壁结垢造成工艺不好控制；精炼机开放式的操作环境烟气 大，环境污染严重，安全性差，脱硫程度低的脱硫胶粉导致能耗较高。
目前行业都积极改进传统的脱硫方式，高温高压动态脱硫罐逐渐被市场淘汰。王京东等(CN 103665428 B连续高温常压脱硫机)是将混有再生剂的废橡胶通过脱硫机内的螺旋输送装置，实现废橡胶的连续、密闭脱硫再生。通过提高脱硫温度达到300℃，将反应时间缩短至15～20min之间。但是由于螺旋结构无法压实物料，传热较差渗透慢，导致再生胶力学性能较差。吕柏源等(CN 103087349 A一种单螺杆热化学、强力剪切复合脱硫设备及其脱硫方法)通过在单螺杆机筒上添加销钉，调整螺纹元件，使得单螺杆出了保持热化学反应功能外，对脱硫的物料进行高剪切作用，强化热化学反应的脱硫效果。物料在单螺杆中并非一直处于压实状态，不可避免的混入氧气，高温条件下橡胶主链降解严重。张立群等(CN102977404B，一种双阶双螺杆挤出机连续制备再生胶的方法)等将废胶粉与再生剂于搅拌机内预处理后，在高温下静置使再生剂充分渗透溶胀胶粉，再加入异向双螺杆挤出机，取代传统的高温高压动态反应罐，脱硫胶粉进入同向双螺杆挤出机，在低温下施加高剪切的作用，取代精炼机。50℃～100℃条件下再生剂粘度仍很高，需要静置12h～36h才能完成渗透，间歇操作生产效率低，高温下保温时间长能耗大；在异向双螺杆内热量仍是由胶粉外部向内传递，不可避免的存在“核—壳”结构，导致力学性能不佳，同向双螺杆精炼过程中的能耗依然很大。
由于受到传热过程和渗透效果的影响，通过化学键的键能差很难实现均匀脱硫，容易产生“核壳”结构，国内外学者对利用化学键的弹性系数差选择性断裂交联键开展了大量工作，取得了很多成果。倪雪文等(CN102888030B废橡胶高温常压再生工艺)不添加任何软化剂和催化剂，直接将胶粉搅拌后通过强制喂料装置压入双螺杆挤出机中施加高温高剪切，实现快速脱硫反应，冷却后的物料加入到变频开放式炼胶机上进行快速剪切，随后在开放式炼胶机中精炼成型，最后经过滤胶后出片。不添加任何助剂的废胶粉粘度高，硬度大，双螺杆加热软化区的温度高达300～350℃才能使胶粉快速软化，不可避免的导致主链的降解，引起再生胶力学性能的下降。汪传生等(CN104004222B一种废橡胶低温连续再生装置及工艺方法)采用密炼机将废胶粉和再生剂进行初步混合解联后，加入双螺杆挤出机进行机械化学反应，通过输送带加入到开炼机上进行精炼，冷却后得到再生胶。开放式的输送装置和精炼设备，污染环境；密炼机间歇生产的物料从的出料口直接排到双螺杆 挤出机的入口，导致会生产过程不稳定。利用化学键的弹性系数差控制合适的剪切可以选择性断裂脱硫，并不存在由于渗透不均匀导致“核壳”结构的问题。
发明内容：本发明的目的在于克服现有单独利用化学键的键能差或化学键的弹性系数差脱硫再生技术的不足，提出一种连续制备再生胶的方法，利用多阶螺杆连续脱硫制备再生橡胶。
本发明的是通过以下流程来实现的：一种多阶螺杆连续脱硫制备再生橡胶的方法，其特征在于该方法包括再生剂的渗透和废胶粉的初步脱硫、脱硫工序和精炼工序联动完成，将废胶粉与软化剂于搅拌机内60℃～120℃下处理5min～25min后，进入60℃～120℃的保温缓冲罐内，经连续密闭保温输送计量装置进入到一台异向双螺杆挤出机内，在100℃～340℃停留1min～6min完成软化剂向胶粉内部的均匀渗透和废胶粉的初步脱硫，再经连续冷却装置在密闭条件下冷却至40℃～80℃，得到门尼粘度为100～230的初步脱硫物料，然后经连续输送至计量加料装置，进入第二台多螺杆挤出机内，通过侧喂料装置加入活化剂，控制多螺杆挤出机的机筒和芯轴的温度在20℃～110℃，1min～6min完成脱硫反应由挤出机挤出门尼粘度为70～150脱硫胶粉，经连续冷却装置在密闭条件下冷却至25℃～60℃，进入第三台多螺杆挤出机内，控制多螺杆挤出机的机筒和芯轴的温度在-5℃～50℃，在剪切条件下精炼1～10min由挤出后，再经成型装置和冷却装置使物料冷却至50℃以下后完成精炼工序，最终包装即可得到所需再生橡胶产品。
废胶粉与软化剂、活化剂的质量比为100:(2～20)：(0.01～3)；
优选的软化剂是煤焦油、芳烃油、松焦油、妥尔油、环烷油、双戊烯、石蜡油、油酸、棉籽油、松香的一种或几者的混合物，活化剂是芳烃二硫化物、多烷基苯酚硫化物、苯基硫醇、胺基化合物的一种或几者的混合物。
所用的废胶粉是废载重子午线轮胎胶粉或废轿车胎胶粉的一种或二者的混合物。
所用的多螺杆挤出机是同向双螺杆挤出机或同向平行三螺杆挤出机中的一种。
优选的的异向双螺杆挤出机的加热排气段温度在120℃～200℃，保温段温度在200℃～340℃，冷却段温度在100℃～200℃。
优选的第二台多螺杆挤出机混合段的机筒温度在40℃～70℃，剪切段的机筒温度在 70℃～90℃，冷却段机筒温度在30℃～60℃。
优选的第三台多螺杆挤出机第一物料输送段的机筒温度在0℃～25℃，预剪切段的机筒温度在5℃～40℃，第二物料输送段的机筒温度在5℃～25℃，第二剪切段的机筒温度在-5℃～35℃，第三物料输送段的机筒温度在0℃～45℃。
本发明合理设计软化剂的渗透和废胶粉的初步脱硫、脱硫工序和精炼工序三者，采用串联的螺杆挤出机作为废胶粉的脱硫再生生产设备，保证了废橡胶再生过程的安全连续化生产。软化剂与废胶粉初步混合后，在异向双螺杆中实现了软化剂的均匀渗透，由于缺少活化剂的作用分子链断裂较少，胶粉颗粒基本都处于均匀溶胀的初步脱硫状态，大分子链处于伸展状态；隔绝氧气加入第二台多螺杆挤出机中，在混合段利用活化剂与软化剂良好的相容性使活化剂均匀分散，在剪切段内温度下活化剂活性较大，通过活化剂和剪切作用实现脱硫再生，冷却后得到均匀脱硫的脱硫胶粉；胶粉经过脱硫后结构发生明显的变化，选择在第三台多螺杆挤出机中低温条件下进行精炼，避免了大分子主链的断裂的同时有效降低脱硫胶粉的门尼粘度，改善加工性能。
将软化剂和活化剂在不同位置依次加入，避免了以往同时加入活化剂和软化剂时，向废胶粉内部边渗透边反应引起的脱硫不均匀；软化剂均匀渗透得到的充分溶胀的胶粉颗粒分子链处于伸展状态，大幅降低了脱硫所需温度，在活化剂和剪切力的双重作用下选择性的打断S-S键，大大提高了脱硫效率的同时保证了力学性能；无核壳结构或硬质颗粒的脱硫胶粉能够快速降低门尼粘度，减少了精炼过程中能耗。
另外，异向双螺杆挤出机正位移输送能力强，可以合理调整渗透时间，具有的自清洁能力避免了长期使用后碳化结垢等引起的工艺变化，产品质量稳定，方便维护保养；在计算机模拟计算的基础上，通过螺纹元件的设计组合使物料在流向、流速上形成多重变化，设计了满足脱硫和精炼的两种要求的多螺杆挤出机，实现了密闭、连续和自动化。通过优化配方和工序，合理设计的装置克服了以往脱硫再生方法的缺陷，大幅降低能耗，整个制备流程在密闭隔氧条件下完成，所得再生胶性能优异，具有操作安全、简单、连续和节能、环保的优点。
附图说明
图1本发明系统示意图
1.保温输送计量装置；2.第一电机，3.第一减速机，4.异向双螺杆，5.异向双螺杆机筒，6.冷却输送装置，7.第二电机，8.第二减速机，9.多螺杆1，10.多螺杆机筒1，11.第三电机，12.第三减速机，13.多螺杆2，14.多螺杆机筒2，15.冷却输送装置，16.包装装置
图2异向双螺杆挤出机示意图
1.电机，2、联轴器，3.减速机，4.异向双螺杆，5.机筒，6.基座
图3同向平行三螺杆示意图
1.电机，2、联轴器，3.减速机，4.双螺杆，5.机筒，6.基座
图4同向双螺杆
1.电机，2、联轴器，3.减速机，4.螺杆，5.机筒，6.基座
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。以下份数没有特别说明均为质量份数。
实施例：
采用废载重子午线轮胎胎面胶粉100份，加入煤焦油10份、松焦油10份为软化剂，于搅拌机内60℃下将胶粉与软化剂混合搅拌8min后，通过连续密闭保温输送计量装置将其加入第一台异向双螺杆挤出机，温度分别设定为加热排气段180℃、保温段为230℃、冷却段160℃，物料在挤出机内停留2min得到门尼粘度为195的初步脱硫胶粉，经冷却输送装置冷却至50℃，然后对接进入第二台同向双螺杆挤出机，从侧喂料加入0.1份活化剂2,2’-二硫化双(6-叔丁基对苯酚)，混合段的机筒温度在45℃，剪切段的机筒温度在70℃，冷却段的机筒温度在35℃，在挤出机内剪切的作用3min由机头挤出后得到门尼粘度110的脱硫胶粉，经过密闭连接冷却装置加入到第三台同向平行三螺杆挤出机，第一物料输送段的机筒温度为15℃，预剪切段的机筒温度为30℃，第二物料输送段的机筒温度为20℃，第二剪切段的机筒温度为25℃，第三物料输送段的机筒温度为15℃，芯轴温度为10℃，在挤出机内剪切的作用3min由机头挤出后，经成型装置和冷却装置使物料冷却至40℃，得到门尼粘度53的再生胶产品。
Figure PCTCN2017118796-appb-000001
实施例2
采用废载重子午线轮胎胎面胶粉100份，加入妥尔油2份、松焦油3份为软化剂，于搅拌机内80℃下将胶粉与软化剂混合搅拌15min后，通过连续密闭保温输送计量装置将其加入第一台异向双螺杆挤出机，温度分别设定为加热排气段160℃、保温段为280℃、冷却段120℃，物料在挤出机内停留5min得到门尼粘度为180的初步脱硫胶粉，经冷却输送装置冷却至60℃，然后对接进入第二台同向双螺杆挤出机，从侧喂料加入3.0份活化剂二苯基二硫，混合段的机筒温度为55℃，剪切段的机筒温度为80℃，冷却段的机筒温度为40℃，在挤出机内剪切的作用3min由机头挤出后得到门尼粘度100的脱硫胶粉，经过密闭连接冷却装置加入到第三台同向平行三螺杆挤出机，第一物料输送段的机筒温度为15℃，预剪切段的机筒温度为30℃，第二物料输送段的机筒温度为20℃，第二剪切段的机筒温度为25℃，第三物料输送段的机筒温度为15℃，芯轴温度为10℃，在挤出机内剪切的作用3min由机头挤出后，得到门尼粘度62的再生橡胶产品。
Figure PCTCN2017118796-appb-000002
实施例3：采用废载重子午线轮胎胎面胶粉100份，加入妥尔油8份、松焦油6份、松香4份为软化剂，于搅拌机内100℃下将胶粉与软化剂混合搅拌20min后，通过连续密闭保温输送计量装置将其加入第一台异向双螺杆挤出机，温度分别设定为加热排气段 160℃、反应段为260℃、冷却段140℃，停留4min后物料挤出后得到门尼粘度为160的初步脱硫胶粉，经冷却输送装置冷却至55℃，然后对接进入第二台同向双螺杆挤出机，从侧喂料加入0.2份的活化剂正丁胺，混合段的机筒温度在65℃，剪切段的机筒温度在90℃，冷却段的机筒温度在50℃，在挤出机内剪切的作用3min由机头挤出后得到门尼粘度90的脱硫胶粉，然后对接进入第三台同向平行三螺杆挤出机，第一物料输送段的机筒温度为5℃，预剪切段的机筒温度为15℃，第二物料输送段的机筒温度为10℃，第二剪切段的机筒温度为20℃，第三物料输送段的机筒温度为15℃，芯轴温度为15℃，在挤出机内剪切的作用2min由机头挤出后，经成型装置和冷却装置使物料冷却至30℃，得到门尼粘度50的再生胶产品。
Figure PCTCN2017118796-appb-000003

Claims (5)

  1. 一种多阶螺杆连续脱硫制备再生橡胶的方法，其特征在于，将废胶粉与软化剂于搅拌机内60℃～120℃下处理5min～25min后，进入60℃～120℃的保温缓冲罐内，经连续密闭保温输送计量装置进入到一台异向双螺杆挤出机内，在100℃～340℃停留1min～6min完成软化剂向胶粉内部的均匀渗透和废胶粉的初步脱硫，再经连续冷却装置在密闭条件下冷却至40℃～80℃，得到门尼粘度为100～230的初步脱硫物料，然后经连续输送至计量加料装置，进入第二台多螺杆挤出机内，通过侧喂料装置加入活化剂，控制多螺杆挤出机的机筒和芯轴的温度在20℃～110℃，1min～6min完成脱硫反应由挤出机挤出门尼粘度为70～150的脱硫胶粉，经连续冷却装置在密闭条件下冷却至25℃～60℃，进入第三台多螺杆挤出机内，控制多螺杆挤出机的机筒和芯轴的温度在-5℃～50℃，在剪切条件下精炼1～10min挤出后，再经成型装置和冷却装置使物料冷却至50℃以下后完成精炼工序，最终包装得到所需再生橡胶产品；
    废胶粉与软化剂、活化剂的质量比为100:(2～20)：(0.01～3)；
    软化剂是煤焦油、芳烃油、松焦油、妥尔油、环烷油、双戊烯、石蜡油、油酸、棉籽油、松香的一种或几者的混合物，活化剂是芳烃二硫化物、多烷基苯酚硫化物、苯基硫醇、胺基化合物的一种或几者的混合物；
    所用的废胶粉是废载重子午线轮胎胶粉或废轿车胎胶粉的一种或二者的混合物。
  2. 根据权利要求1所述的方法，其特征是所述多螺杆挤出机是同向双螺杆挤出机或同向平行三螺杆挤出机中的一种。
  3. 根据权利要求1所述的方法，其特征是：异向双螺杆挤出机的加热排气段温度在120℃～200℃，保温段温度在200℃～340℃，冷却段温度在100℃～200℃。
  4. 根据权利要求1所述的方法，其特征是：第二台多螺杆挤出机混合段的机筒温度在40℃～70℃，剪切段的机筒温度在70℃～90℃，冷却段机筒温度在30℃～60℃。
  5. 根据权利要求1所述的方法，其特征是：第三台多螺杆挤出机第一物料输送段的机筒温度在0℃～25℃，预剪切段的机筒温度在5℃～40℃，第二物料输送段的机筒温度在5℃～25℃，第二剪切段的机筒温度 在-5℃～35℃，第三物料输送段的机筒温度在0℃～45℃。
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