CN100558762C - Process for making halogenated rubber-like polymers - Google Patents

Abstract

The present invention relates to a new method for the manufacture of halogenated rubbery polymers, comprising the reaction of unsaturated rubbery polymers with a halogenating agent, characterized in that the halogenation reaction is controlled by adding in a closed drying system of a screw and screw extrusion reactor A large amount of raw materials and additives are continuously and sequentially plasticized, degassed, softened, multi-stage halogenated, stabilized, devolatilized, and cut into pieces so that the process does not produce waste water and waste gas containing acid and salt. The halogenated rubber-like polymer has controllable halogen content and does not contain corrosive acid gas. It is a new generation method for manufacturing halogenated rubber-like polymers and can replace the current production equipment and methods of halogenated butyl rubber and ethylene-propylene rubber.

Description

Process for making halogenated rubber-like polymers

technical field

The invention relates to the field of producing synthetic rubber, in particular to an environment-friendly and energy-saving method for producing halogenated rubber-like polymers.

Background technique

The traditional and current production of halogenated butyl rubber or halogenated EPDM rubber, etc., all adopt the solution method, and there are three types of process routes. The first method: make solid butyl or ethylene-propylene rubber in the preparation kettle to make butyl and other rubber solutions with a hexane or carbon tetrachloride rubber content of about 15% (wt), and then in the halogenation reaction kettle, with the added Gas-phase or liquid-phase halogen reaction. After halogenation, it is washed with alkali to neutralize the by-product hydrogen halide and a small amount of excess halogen contained in the glue, and then washed with a large amount of water to neutrality. After washing, the upper organic solution rubber phase is recovered. Add The anti-aging agent meets a large amount of steam, the separated solvent is evaporated from the top, and is recycled and used. After the water glue is dehydrated by a vibrating screen, it is dehydrated by extrusion and expanded by extrusion to reduce the volatile matter to 1 % (wt) or so, cut into pieces, packaged and put into storage. This kind of production route makes the choice of production factory address flexible, and is not limited by the conditions of raw material factories. The second method must be connected with rubber production devices such as butyl, use the hydrothermal rubber particles (clusters) after stripping as raw materials, and use hexane in a dissolution kettle to prepare rubber 15-16% (wt) Concentrated rubber solution containing saturated water is pumped to dehalogenate, then washed with alkali and water, and then the sewage is separated, stripped, extruded, dehydrated and dried to obtain rubber products such as halogenated butyl. Above-mentioned two kinds of technological routes, only one is dry rubber piece on raw material, and the latter one is wet rubber piece, and other processes are all identical. The third method: the so-called solvent replacement method, which is based on the slurry of butyl rubber in methyl chloride from the polymerization tank of the butyl rubber production plant as a raw material, and in the flash tank, feed 150-130 ℃ of hexane vapor, use hot hexane to bring heat to distill out low-boiling methyl chloride and unreacted monomers to form a butyl rubber hexane solution, which is then properly concentrated to a butyl rubber solution containing 18% (wt) , pumped out to carry out the halogenation reaction, after which the reactants go through the same steps as the above two process routes to obtain halogenated butyl rubber products. This method must be integrated with a general-purpose butyl rubber manufacturing device. Compared with the first and second methods, it saves several steps of steam stripping and drying, and the cost is slightly lower, but the product purity is slightly worse. Above-mentioned existing three kinds of industrial production methods are characterized in that:

1. In the halogenated stirred tank, the halogenated raw materials are solutions with a low concentration of 15-18% (wt) rubber solid content. Under the condition of a weight ratio of 1000:6 between a large amount of high-viscosity matter and a small amount of low-viscosity matter (gas or liquid), To complete the halogenation reaction, in addition to consuming a large motor power to enhance the stirring effect, the process operation cost is also high, and the overall reaction efficiency of this method is low, especially when bromine chlorination and bromination reactions are carried out at lower temperatures The disadvantages are more significant.

2. Hydrogen halide, a by-product of the halogenation process, cannot be recycled, especially hydrogen bromide, which consumes a large amount of alkali, and produces a large amount of saline waste water and acid waste gas. One ton of product produces 10-25 tons of waste water, wasting water resources. And caused environmental pollution, this situation runs counter to the development of modern society. In addition, under the condition of hot alkaline water, the allyl halide on the halogenated rubber is prone to hydrolysis reaction, resulting in fluctuations in product quality.

3. The whole process is carried out in the presence of a large amount of water, resulting in serious corrosion of halogenated hydrogen acids. Pipelines, valves, equipment, instruments, pumps, electrical appliances and workshops, etc. must meet the requirements for preventing halogenated acids, so that the production equipment and The process becomes very complicated, and acid-resistant high-nickel alloys are also used, which greatly increases the total investment, and the costs of operation, protection and maintenance are also greatly increased, resulting in high costs.

4. In order to get rid of hydrogen halide by-products, the whole production process is elongated, and there are many auxiliary equipments, which increases the production operation cost and high energy and material consumption.

In addition to halogenated butyl, chlorinated EPDM, chlorosulfonated polyethylene, chlorinated cis-butyl and halogenated polyisoprene, etc., mostly use the solution method of halogenation, alkali neutralization, water washing and stripping, etc. Processing technology, therefore all there is above-mentioned similar problem. Especially using chlorinated hydrocarbons as solvents, using the above process, the recovery rate of solvents is low, and the discharge into the atmosphere will destroy the ozone layer and seriously affect the environment on which human beings live.

Contents of the invention

The purpose of the present invention is to overcome many disadvantages existing in the above-mentioned prior art, especially to solve the problems of severe environmental pollution, device corrosion, long flow process, high energy and material consumption and low product purity. After the inventor has been engaged in the development and research of synthetic rubber for a long time And industrial production practice, in order to solve the above problems, develop and provide a new method of manufacturing halogenated rubber-like polymers with unique process technology, no system corrosion and environmental pollution, controllable halogen content of the product and no free acid.

The method for producing halogenated rubber-like polymers provided by the invention includes reacting unsaturated rubber-like polymers with halogenating agents, and is characterized in that the whole process is in a closed drying system of a screw and screw extrusion reactor, and the unsaturated rubber-like Polymers and corresponding additives are continuously and sequentially plasticized or mixed, degassed, softened, multi-stage halogenated (preferably three-stage or four-stage halogenated), stabilized, devolatilized, and metered and cut into pieces, so that the process does not contain Acid, salt waste water and waste gas, halogenated rubber-like polymers have controllable halogen content and no corrosive acid gas.

In the method for producing halogenated rubber-like polymers provided according to the present invention, the unsaturated rubber-like polymers (referred to as polymers or rubbers) refer to polymer chains containing a certain amount of unsaturated double bond structural units or active Functional rubber-like polymers such as butyl rubber, star-branched butyl rubber, EPDM rubber, polyisoprene rubber, polybutadiene rubber, natural rubber, styrene-butadiene rubber, styrene-butadiene block Copolymer or isobutylene and methyl styrene copolymer rubber, etc. These rubbery polymers usually have two kinds of solid and liquid. The solid bulk rubber (commercially available) is cut into planned or irregular rubber blocks (granules) <50mm for use. The liquid raw material is preferably rubber liquid produced online by a synthetic rubber production device or a saturated hydrocarbon solution with a polymer solid content of 15-30% (wt). For example, the unsaturation of butyl rubber is 0.5-2.5%, Mooney viscosity ML1+4, and 22-60 at 100°C. Different varieties of butyl rubber have different specifications, usually within the above range. The unsaturation of EPDM rubber is 1.2-2.3%, the Mooney viscosity is ML1+4, and the temperature is 30-95 at 100°C. For other rubbery polymers such as homopolymers of butadiene, isoprene or copolymers with styrene etc., the degree of unsaturation (unit structure) should be at least 15%.

In the method for producing halogenated rubber-like polymers provided according to the present invention, the halogenating agent is known chlorine gas, hydrogen chloride, bromine chloride gas, liquid bromine or halogen-carrying chemicals such as activated carbon for adsorbing bromine, etc., these halogenating agents must be It enters the system after dehumidification treatment. The halogenation reaction between unsaturated rubbery polymer and halogenating agent is mainly carried out by replacing hydrogen atoms on carbon atoms with halogenating agent, so the amount of halogenating agent is twice the amount of rubbery polymer. times. In addition to the by-product consumption of the reaction, the amount of halogenation used for the halogenation reaction should be 0.4 to 1.2 times the molar percent of the unsaturation of the halogenated rubber-like polymer. Excessive halogenating agents will cause the rubber-like polymer to be greatly divided into the main chain. The carbon-carbon bond is broken, resulting in oligomer products, which seriously impairs the properties of halogenated rubber-like polymers. The dosage of the halogenating agent is 0.9-1.05 times of the halogen content that the halogenated product should reach. The characteristics of the halogenation reaction of the present invention are continuous and multi-stage, preferably three or four stages, and the amount and flow rate of the halogenating agent are very small. In order to improve the metering accuracy and eliminate the uneven reaction phenomenon of excessive local concentration, a diluent is added to the halogenating agent. , The gas phase diluent is an inert gas, and the diluent is required not to participate in and hinder the halogenation reaction under the halogenation conditions of this system, and not to liquefy under the corresponding reaction pressure.

The inert gas diluent is nitrogen, methane, ethane, propane, carbon dioxide and the like. The volume ratio of halogenating agent to diluent gas is 1:0.1~30, which can be selected according to the feeding conditions. The ratio of feeding positions of different halogenating agents can be changed to obtain a stable and balanced halogenation reaction. The inert gas also acts as a safety blanket for the halogenating agent system.

According to the present invention, in the method for producing halogenated rubber-like polymers, the screw and screw extrusion reactor (reactor for short), including the screw device of unsaturated rubber-like polymer feed (referring to 3, 8 and attached in the figure Auxiliary equipment) are composed of two parts: a fixed outer cylinder and a rotating shaft. The outer cylinder has a cold medium channel and a hot medium jacket, the screw machine cylinder is composed of 1-5 sections connected, and the screw extrusion reactor cylinder is composed of 6-20 sections connected by flanges. Each section uses cold and hot media to control the temperature. According to the needs of the halogenation reaction, the cylinder is equipped with functional orifices for feeding, exhausting, temperature measurement, pressure measurement and sampling.

The rotating shaft in the cylinder is divided into two categories: uniaxial and biaxial, and the whole is called screw extruder (Figure 1):

e.g. single screw and screw extrusion reactors, diameter ~600mm; length-to-diameter ratio L/D 5~30; shaft speed 20~300 rpm, speed adjustable;

～250mm，长径比L/D 25～45，轴转速50～500转/分，可调速；Intermeshing co-rotating twin-screw extrusion reactor, with the strongest self-cleaning ability, diameter

~250mm, length-to-diameter ratio L/D 25~45, shaft speed 50~500 rpm, adjustable speed;

～300mm，长径比L/D 40～100，轴转速30～500转/分可调速；Non-intermeshing or/and intermeshing reverse twin-screw extrusion reactors, offering minimal shear strength, diameter

~300mm, length-to-diameter ratio L/D 40~100, shaft speed 30~500 rpm adjustable;

～1000mm，长径比L/D 5～10，主轴转速10～100转/分，可调速等。Self-cleaning double-helix asynchronous concentration reactor, diameter

~1000mm, length-to-diameter ratio L/D 5~10, spindle speed 10~100 rpm, adjustable speed, etc.

The type of agitator on the above-mentioned rotating shaft and the spiral or thread shape, the number of threads, the depth of the screw groove, the geometric dimensions such as pitch and screw edge, in the reactor of the present invention, along with the requirements of the process for plasticizing (mixing), degassing, The steps of softening, multi-stage halogenation, stabilization, devolatilization, metering, discharging and slicing have different functions, and corresponding changes are made to adjust the force between the material and the inner wall of the cylinder, the screw or the screw and the material, and realize the control of the pressure and temperature of the material. Effective control, so that the process and reactor equipment are closely combined to optimize. In the halogenation reaction section, due to the increase of the polymer concentration and the action of the high-speed screw, the number of contact times per unit time between the halogenating agent and the polymer reaction point has been increased by several orders of magnitude, and the apparent reaction rate has been increased by about 10 times. Viscous stream interacts with a small amount of low-viscosity fluid to obtain high efficiency of halogenation reaction.

The reactor provided by the present invention has a collective structure and includes 7 consecutive sequential steps, and the space occupied by each step can be adjusted according to different products, which is also a feature of the present invention.

The composition and configuration of the reactor vary with the different unsaturated rubbery polymers. When the raw material is a viscous hydrocarbon solution with a polymer content of 15-30% (wt), the reactor consists of a screw and a One or several screw extruders, or set the length of the screw according to the process requirements and the ability to manufacture the screw extruder. The polymer solution removes most of the solvent and a small amount of unreacted monomers in the double-screw concentrator (8), increases the solid content to 50-70% (wt), and then sends it into the reaction system of the screw extruder. The double-helix concentrator has a self-cleaning function. In addition to continuously updating the surface of the mixed material, the material is also slowly pushed forward by the helical agitator. Control the residence time, material temperature and evaporation space pressure to limit the amount of discharged solvent and maintain the specified solid concentration. And if the raw material is fragments of solid rubber, the advanced screw crushing feeder (3) will continue to crush and reduce the size of the lumps on the one hand, and also play a plasticizing role on the other hand, so as to facilitate entry into the screw extrusion reactor system ( see picture 1).

According to the method for producing halogenated rubber-like polymers provided by the present invention, the halogenated product manufacturing process is continuously and sequentially plasticized ( Mixing), degassing, softening, multi-stage halogenation, stabilization, devolatilization, metering and cutting into blocks, wherein the five steps also need to add corresponding additives in sections to ensure that the chlorine content of the halogenated rubber-like product with a qualified structure in the present invention is achieved. And/or bromine content and Mooney viscosity are strictly controlled within the required range.

The plasticizing or mixing step is a solid unsaturated rubbery polymer or unsaturated rubbery polymer solution such as butyl rubber or ethylene propylene rubber hydrocarbon solution produced on-line with a size of <50mm, in the plasticizing section with inert gas If pure N ₂ is fully mixed at 70-110°C, preferably 80-90°C for plasticization or mixing, the pressure of N ₂ is 0.01-0.1MPa, and the flow rate is 3-6 times the volume flow rate of the feed.

The degassing step is plasticized or mixed material (unsaturated rubber polymer), after being depressurized at the exhaust port of the degassing section, _the non-condensable gas, moisture, low Boiling point hydrocarbons or unsaturated monomers may be produced to ensure that the degassed materials meet the requirements, such as oxygen and water below 20PPm, and enter the downstream steps.

The softening step is to add softeners such as solvents, plasticizers and lubricants to the softening section of the degassed material for thorough mixing, and the amount added is 0.1-1.0 times the weight of the polymer.

The multi-stage halogenation step is carried out in the multi-stage halogenation section of the reactor. During the halogenation process, the softened unsaturated rubber-like polymer material in the softening section and the halogenating agent diluted with pure nitrogen diluent undergo multi-stage halogenation reactions, preferably three stages. The one-stage or four-stage halogenation reaction is mainly to replace the carbon-bonded hydrogen atoms on the polymer chain with halogen, and add a small amount (or no) of double bonds. Process conditions can be selected under a wide range of conditions, the temperature range is 0-165 ° C, and the pressure is 0.2-10 MPa. When gas-liquid reaction, it is beneficial to increase the pressure, and the screw and screw extrusion reactor used in the present invention have the characteristics of higher resistance Due to the characteristics of high pressure, if necessary, the halogenation reaction of rubber-like polymers can be realized under the supercritical conditions of some macromolecular co-solvents such as carbon dioxide. Halogenation process conditions, under the concentration range conditions of the above-mentioned two reactants of the inventive method, are different according to products and raw materials, such as chlorinated butyl rubber, its halogenation reaction temperature is 30-130 ° C, and the pressure is 0.3-8.0 MPa; bromine chlorination Butyl rubber, halogenation reaction temperature 0～120℃, pressure 0.3～5.0MPa; Bromobutyl rubber, halogenation reaction temperature 10～150℃, pressure 0.3～4.0MPa; Chlorinated EPDM rubber, halogenation reaction temperature 30 ～140℃, corresponding pressure 0.6～6.0MPa. The halogenation reaction of the present invention has the characteristics of multiple times, batches and continuous addition. The halogenation dose, temperature and pressure of each stage can be adjusted as required. The halogenation reaction is continuous and carried out in multiple stages. Its significant advantage is to reduce the initial halogenation. The intensity of the reaction makes the reaction process uniform and reduces the 5%-10% breakage of the main chain of the macromolecule that is common in the current halogenation technology, thereby improving the product quality. For example, three-stage halogenation, the amount of halogenating agent added to each stage is 50, 30, 20%, and the reaction temperature is 30-60°C, 60-110°C, 110-140°C; four-stage halogenation, the amount of halogenating agent added to each stage The amounts are 40, 30, 20, and 10%, respectively, and the halogenation temperatures are 0-50°C, 60-100°C, 110-130°C, and 130-150°C.

The amount of the halogenating agent used in the above-mentioned halogenation reaction process is 0.4-1.2 times of the unsaturation (mol%) of the unsaturated rubber-like polymer. The volume ratio of the halogenating agent to the diluent such as _N2 is 1:0.1-30.

The stabilization step is to add stabilizers and anti-aging agents to the stabilized section of the reactor after the halogenation, the addition of stabilizers such as epoxy soybean oil is 0.05-5%, and the anti-aging agent 264 is 0.05-2% (wt) (polymer );

The devolatilization step is carried out in 2-4 stages of devolatilization. In the devolatilization stage, auxiliary devolatilizers such as _N2 or CO2 are respectively added _to remove HCl, _N2 , a small amount of chlorine and low boiling point substances. The addition amount is 1-20% (wt) of the polymer, and the number of devolatilization stages varies with its process conditions, raw material properties and product requirements. Second-stage devolatilization conditions: the first-stage devolatilization temperature is 80-120°C, and the pressure is 30-60KPa; the second-stage devolatilization temperature is 120-160°C, and the pressure is 20-40KPa. Four-stage devolatilization conditions:

The first devolatilization temperature is 60-100°C, the devolatilization pressure is 60-80KPa,

The second-stage devolatilization temperature is 100-120°C, the devolatilization pressure is 60-40KPa,

The third stage devolatilization temperature is 120-140℃, devolatilization pressure is 40-20KPa,

The fourth-stage devolatilization temperature is 140-180°C, and the devolatilization pressure is 10-20KPa;

Exhaust gases are recovered and reused separately.

Described additive kind and consumption range are as follows respectively:

1. Softener: C ₆ -C ₈ raffinate oil, industrial hexane, cyclohexane, heptane, solvent gasoline, paraffin oil, naphthenic oil; sebacate, adipate, azelate, Phosphate esters; paraffin waxes, microcrystalline waxes, mixed waxes, stearamide waxes; low molecular weight polyethylene; stearic acid and its salts. The first five kinds of raffinate, industrial hexane, cyclohexane, heptane, solvent gasoline and other low boiling point substances are added in an amount of 0.1-1.0 times the weight of the polymer. High boiling point substances such as paraffin oil and naphthenic oil are 0.1-0.3 times the weight of the polymer. The softener can be used alone or in combination (in any proportion), and the weight ratio of the total amount of the two to the polymer is 0.1-1.2/1. The amount of sebacic acid ester, adipate, azelaic acid ester and phosphoric acid ester is 0.2-0.05 times of the weight of the polymer. Paraffin wax, microcrystalline wax, mixed wax, stearamide wax, the dosage is 0.05-0.25 times of polymer weight. Low-molecular polyethylene (relative molecular weight 1000-8000), the dosage is 0.03-0.05 times. Stearic acid and its salts are used in an amount of 0.01-0.05 times the weight of the polymer. The general addition amount is 0.1-1.0, which varies with the Mooney viscosity of the raw material polymer and the type of softener. For high Mooney materials, the amount of softener should be increased to meet the halogenation requirements. These softeners can be used alone, preferably compounded (in any proportion), the purpose is to minimize the total amount of softeners when the process conditions are met.

2. Degassing and devolatilization aids: All inert gases that do not react with halogens under the halogenation conditions of rubber-like polymers, are easy to obtain locally and are cheap, and can be used as degassing and devolatilization aids. Such as nitrogen, methane, carbon dioxide. The addition amount is 0.01-0.2 times of the volume of the polymer fluid, and it is added during the steps of degassing and volatilization.

3. Stabilizer: The function of the stabilizer is to protect the halogenated rubber-like polymer from breaking the macromolecular chain and removing the combined halogen during devolatilization heating or overhalogenation. Affect the application properties of products. The halogenated products are different, the process conditions of halogenation, devolatilization and metering and pelletizing are different, and the stabilizers and their amounts used are also different. Some stabilizers have dual functions, both stabilizing and improving flow conditions, so they can be added and used multiple times, but the amount of addition is different. The following stabilizers can be used alone or in multiple compound combinations (in any proportion). Generally, the total amount is not large. Its kind and consumption (weight %) are as follows:

Epoxidized soybean oil, the addition amount is 0.5-5%; adipate, sebacate, azelate, the addition amount is 0.5-3%; paraffin wax, microcrystalline wax, the addition amount is 0.5-2%, such as paraffin 1-2%, low molecular weight polyethylene, adding 1-5%; stearic acid and its calcium, potassium, zinc salts, adding 0.05-2%; aliphatic hydrocarbon epoxy resin 1.0-5%; anti-aging Agent: For example, the commercially available brand name is:

264 - 2,6-di-tert-butylcresol,

2246——2,2′-methylene-bis(4-methyl-6-tert-butyl)phenol,

1076——octadecyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,

1010——Tetrakis[methylene β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester,

168——tris(2,4-di-tert-butylphenyl)phosphite,

1520L——2,4-bis[(octylthio)methyl]o-methyl ester,

5652——(4-Hydroxy-3,5-di-tert-butylaniline)-4,6-bis(n-octylthio)-1,3,5 triazine,

136—benzofuranone,

TNPP——tris(nonylphenyl)phosphite, etc., the dosage is 0.05%～1.0%.

According to the method for producing halogenated rubber-like polymer provided by the present invention, the halogenated rubber-like polymer product, for high saturation and low halogen content rubber-like polymer is:

Chlorinated butyl rubber, its chlorine content is in the range of 1.0-1.5% (mass), and the Mooney viscosity is in the range of 30-60;

Bromobutyl rubber, its bromine content is in the range of 1.5-2.5% (mass), and the Mooney viscosity is in the range of 22-50;

The bromochlorobutyl rubber has a bromine content in the range of 1.0-3.0% (mass), a chlorine content in the range of 0.03-0.08%, and a Mooney viscosity in the range of 22-55.

Chlorinated EPDM rubber, its chlorine content is 0.8-1.8% (mass) and middle chlorine content is 13-23%, and its Mooney viscosity is in the range of 30-95.

For rubber-like polymers with high unsaturation and high halogen content, such as chlorinated polybutadiene, chlorinated styrene-butadiene copolymer, chlorinated polyisoprene and natural rubber, the unsaturation is above 15%, The chlorine content of the halogenated product has a wide range from 10 to 66% (mass), while ML1+4, 100°C, generally ranges from 35 to 65. The main purpose of these chlorinated rubber-like polymers is to increase product polarity, improve compatibility and adhesion with related materials.

The present invention provides a new method of making halogenated rubber-like polymers, which is characterized by:

1. The technological process and equipment are reasonable and advanced, with a wide range of applications, which can meet the needs of halogenation reactions of various unsaturated rubber-like polymers or other high polymers, and can adapt to the requirements of both solid and liquid raw materials.

2. The screw and screw extrusion reactors used are suitable for various requirements of high-efficiency transportation, mixing, mass transfer, heat transfer, degassing and devolatilization of high- and medium-viscosity fluids, and are especially suitable for bulk and high-solid-content rubber-like The macroscopic reaction rate of the halogenation reaction of high-viscosity polymer and low-viscosity small amount of halogen is increased by an order of magnitude compared with the traditional tank-type halogenation reaction.

3. The present invention concentrates the rubber-like polymer halogenation process in a very compact and continuous process of plasticizing (mixing), degassing, softening, multi-stage halogenation, stabilization, devolatilization, metering and cutting into pieces, seven steps Realized in a closed drying system, compared with the traditional halogenation production process, the process flow is shortened by 3/4, saving investment and energy and power consumption. More importantly, by-product hydrogen halide is recovered reasonably, saving alkali for neutralization, no serious corrosion of equipment, no acid waste gas and a large amount of salty waste water, which fundamentally improves the production status of halogenated rubber and is very beneficial to environmental protection; halogenated rubber The halogen content of the polymer is controlled, and it does not contain corrosive acid gas.

4. The ingenious combination of the multi-stage halogenation process of the present invention and the screw extrusion reactor, plus the addition of halogenation agent, temperature and pressure can be adjusted in stages, which can ensure the efficient and stable progress of the halogenation reaction, avoiding and reducing the main chain of macromolecules The occurrence of the degradation side reaction of fracture due to overhalogenation is conducive to the improvement of the internal quality of halogenated polymer products, which is difficult to achieve in the current traditional rubber and plastic halogenated production technology, and is also a major advantage of the halogenated polymer technology of the present invention.

Description of drawings

Figure 1 is a schematic diagram of the process flow for producing halogenated rubber-like polymers, and the illustrations are as follows:

Solid rubber particles or broken raw material feeding line 1, low-pressure nitrogen pipeline 2, screw crushing plasticizer 3, sealed chlorine gas 4, liquid rubber raw material pipe 5, liquid raw material buffer tank 6, preheater 7, double-screw concentrator 8, Booster pump 10, reactor plasticizing/mixing section 9, recovered hydrocarbon steam 11, reactor degassing section 12, recovered hydrocarbon steam 60, exhaust machine 61, buffer separation tank 62, medium pressure pure nitrogen pipeline 63, high boiling point Plasticizer pipe 13, low boiling point softener pipe 14, stirring homogenizer 15, metering pump 16, reactor softening section 17, inert gas 18, halogen gas 19, mixing buffer 20, booster 21, pre-halogenation Reaction section 22, regulator pipeline 23, liquid halogen pipeline 24, mixing tank 25, metering pump 26, intermediate halogenation reaction section 27, post-halogenation reaction section 28, solvent pipeline 29, stabilizer 30, mixing tank 31, metering feeding Pump 32, reactor stabilization section 33, reactor devolatilization section 34, 37, auxiliary devolatilization pipes 35, 36, dry hydrogen halide recovery line 38, cooling condenser 39, condensate tank 40, low boiling point recovery pipe 41 , steam cooler 42,44, vacuum exhauster 43, reactor discharge metering section 45, product slice (granule) machine 46, halogenated rubber-like product 47, reactor temperature monitoring point 48-55,64,65, pressure Monitoring Point, 56-59.

Detailed ways

The present invention is further illustrated with the following examples, but the protection scope of the present invention is not limited to the following examples.

Example 1:

排气口，物料被降压，氮气夹带空气、潮气和可能的不饱和单体或低沸点烃，被排气机

抽出，控制缓冲分离罐

的压力和中压纯氮

量，以保证脱气后原料达到要求。脱气后进入反应器软化段

在搅拌均化釜

加入0.2倍橡胶重量的环己烷

和0.1倍橡胶重量的环烷烃油

0.01倍橡胶重量的己二酸酯的软化剂，三种软化剂用前均进行脱去微量水和氧的处理，平均在20PPM以下。上述按比例混均匀后的混合软化剂，用计量加料泵

增压加入软化段，料温将降低到60～70℃，在混合缓冲器

以0.45Kg氯气/纯氮按体积1/10比配成卤化剂，按50％、30％、20％比例，按次加入前、中、后卤化反应段

反应属低放热过程，温度易控，前卤化反应温度50～70℃，中卤化反应温度70～100℃，后卤化反应温度90～130℃。卤化反应段占据了螺杆挤出反应器40％空间，保证了卤化反应足够时间和卤化剂近99％以上利用率。在混合釜

用0.1倍橡胶重量的环己烷0.005倍橡胶重量的酚类防老剂2246和0.01倍橡胶重量的硬脂酸钙，配制成稳定剂溶液，再用计量加料泵

压入反应器的稳定段

在两个脱气段

分别通入橡胶量5～10％的纯氮，第一脱挥口温度130℃左右，压力50KPa。第二脱挥口温度150℃左右，压力20KPa。排除的含氯化氢、氮、少量氯气和低沸点溶剂，经冷却器降温后，用排气机

增压，再经冷凝器

回收溶剂后，纯干卤化氢气体回收利用。Using the process flow shown in Figure 1, the main equipment of the closed drying system in this embodiment is a reverse twin-screw extruder unit (reactor), the screw diameter is Φ36mm, and the length-to-diameter ratio L/D=60, except for the metering discharge section Except for meshing, the rest of the segments are non-meshing. The cylinder body is divided into 10 sections for temperature control, the internal cooling medium of the cylinder is 0 ℃ white oil, and the outer cylinder is heated by an electric heating copper tile heating jacket. The raw material used is chopped solid butyl rubber fragments or strips, and its maximum outline dimension or cross-section is less than 20mm. Add the hopper of the spiral crushing plasticizer ③, the weight is 30kg, its specification is unsaturation 2%, Mooney 34 commercially available general-purpose butyl rubber. In the lower part of the hopper, 0.01MPa pressure nitrogen gas is continuously introduced, and the flow rate is about 0.2NM ³ /h. Spiral crushing and plasticizing machine ③, the temperature is controlled at 50-80°C, the rubber is shredded and extruded into porous softened and non-sticky flocs, which are sent to the downstream reaction system. nitrogen. In the plasticizing (mixing) section ⑨ of the reactor, twin-screw screws with cutting and mixing functions are arranged staggeredly to plasticize the softened raw materials, and at the same time, pure nitrogen is introduced to mix with the materials. The temperature of the plasticizing section can be controlled. At around 90°C. In the reaction degassing section

The exhaust port, the material is depressurized, the nitrogen entrains air, moisture and possible unsaturated monomers or low boiling point hydrocarbons, and is exhausted by the exhaust machine

Extraction, control buffer separation tank

pressure and medium pressure pure nitrogen

To ensure that the raw materials meet the requirements after degassing. After degassing, it enters the softening section of the reactor

stirring homogenizer

Add 0.2 times the weight of rubber cyclohexane

and 0.1 times the rubber weight of naphthenic oil

0.01 times the rubber weight of the adipate softener, the three softeners are all treated to remove traces of water and oxygen before use, and the average value is below 20PPM. The mixed softening agent after the above-mentioned uniform mixing in proportion is used by a metering feeding pump

Pressurization is added to the softening section, and the material temperature will drop to 60-70°C. In the mixing buffer

Use 0.45Kg chlorine/pure nitrogen to prepare a halogenating agent at a ratio of 1/10 by volume, and add it to the front, middle, and rear halogenation reaction sections in sequence at 50%, 30%, and 20% ratios

The reaction is a low exothermic process, and the temperature is easy to control. The pre-halogenation reaction temperature is 50-70°C, the middle-halogenation reaction temperature is 70-100°C, and the post-halogenation reaction temperature is 90-130°C. The halogenation reaction section occupies 40% of the space of the screw extrusion reactor, which ensures sufficient time for the halogenation reaction and nearly 99% utilization rate of the halogenation agent. in the mixing kettle

Use 0.1 times the weight of rubber cyclohexane 0.005 times of rubber weight of phenolic anti-aging agent 2246 and 0.01 times of rubber weight of calcium stearate are prepared into stabilizer solution, and then the metering pump is used

Press into the stable section of the reactor

in two degassing sections

5-10% of the rubber content is fed into pure nitrogen respectively, the temperature of the first devolatilization port is about 130°C, and the pressure is 50KPa. The temperature of the second devolatilization port is about 150°C and the pressure is 20KPa. Excluded solvents containing hydrogen chloride, nitrogen, a small amount of chlorine and low boiling point, through the cooler After cooling down, use the exhaust machine

Pressurized, then through the condenser

After recovering the solvent, the pure dry hydrogen halide gas is recycled.

切块并闪蒸降温，得到氯含量1.1％(质量)，门尼粘度38的氯化丁基产品，本产品含有环烷油4.3％(wt)，在做制品加操作油时可扣除，产品具有很好的综合物性和加工性。其挥发物含量＜0.2％(wt)，不含游离卤化物。上述连续卤化系统，每小时可得氯化丁基橡胶22.7kg产品，回收可循环使用的干环己烷6kg，消耗氯气0.45kg，回收干氯化氢气体0.23kg，可压力装瓶作为付产品出售或用于其它橡胶或化学品的卤化剂。Chlorinated butyl rubber from which by-produced hydrogen halide has been removed, passed through the metering section The steady flow, cooling and boosting pressure is sent to the outlet template, where it passes through the die surface cutting machine

Cutting into pieces and flash cooling to obtain chlorine content of 1.1% (mass), Mooney viscosity 38 chlorinated butyl product, this product contains naphthenic oil 4.3% (wt), can be deducted when making products and adding process oil, product It has good comprehensive physical properties and processability. Its volatile matter content is less than 0.2% (wt), and it does not contain free halides. The above-mentioned continuous halogenation system can obtain 22.7kg of chlorinated butyl rubber per hour, recover 6kg of recyclable dry cyclohexane, consume 0.45kg of chlorine gas, and recover 0.23kg of dry hydrogen chloride gas, which can be sold as by-products by pressure bottling or Halogenating agent for other rubbers or chemicals.

Example 2:

与实施例一不同，进入塑化段的粘稠溶液，只与少量氮气

混合，在排气口处的缓冲分离罐

的压力被控制得较高，而温度较低，以防止大量溶剂被蒸发。随原料改变，软化剂组成改为环己烷/己二酸酯/环烷油0.1/0.05/0.05重量比例。在搅拌均化釜均化后，用计量加料泵加到反应软化段

在此将物料降温到50℃左右。混合缓冲罐

夹套通0℃冷油降温至5℃左右，配好的氯化溴气体维持于7～5℃，并用纯氮稀释10倍，然后将加入量按60％、30％、10％分别连续加入前、中、后卤化反应段前卤化段温度5～30℃，中卤化段温度50～70℃，后卤化段温度则上升到70～120℃。将环氧大豆油、2264、混合石蜡和环己烷，以橡胶质量为100，按0.5/0.1/0.5/5比例配成溶液，连续用计量加料泵注入反应稳定段

在脱挥段分别从脱挥助剂口加入卤化橡胶物料体积5％的氮气，压力维持在3.0～5.0MPa，第一排气口压力50KPa左右，温度110～130℃调节。第二排气口压力20KPa左右，温度在120～150℃调节，以确保卤化产品中游离卤素和低沸物的脱除。本实施例2，所得产品为溴氯化丁基橡胶，每小时产量34.1kg(含8.8％操作油)，产品溴含量2％质量，氯含量0.5％质量，门尼粘度42左右。产品耐热性和颜色稳定性都比单卤化产品有一定改善。但由于氯化溴要求低温保存，能耗高、操作也比较复杂。而本发明具有克服这个弊病的条件和方法，即利用多段卤化技术，改变上述加料方式，在前卤化段加入含氯氮气，使聚合物含有0.1～1％质量的氯元素。而在中、后卤化反应段加入液体溴，使聚合物又含有溴元素，其量在1～2.5％质量范围。而各段反应温度能分别提高，前卤化段

的氯取代反应，温度为60～80℃，中卤化段溴化反应反应温度40～60℃，后卤化段

反应温度70～110℃。经过稳定化和脱挥，所得产品，其溴含量1.9％质量，氯含量0.8％，门尼粘度44。连续化产量可在18～36kg/小时范围调节。The same reactor as in Example 1 was used to close the drying system. But the raw material used in this embodiment is butyl rubber hexane solution with a solid content of 18% (wt) pumped from ⑤, the unsaturation of the dry glue is 2.2%, and the Mooney viscosity is 50. The inside of the tank is under the protection of positive nitrogen pressure. The glue liquid flows out from the raw material buffer tank ⑥, is heated to 150℃～160℃ by the preheater ⑦, and enters the double-screw concentrator ⑧. The solvent and a small amount of water are evaporated and recovered. The viscous solution concentrated to a solid content of about 70% is sent into the halogenation reaction system by the booster pump ⑩. Double-helix concentrator⑧, is a double-helix asynchronous and synchronous concentration reactor with a diameter of Φ100 and L/D=10. Its jacket has a heating function to keep the polymer raw material at a higher temperature so as to enter the halogenation reaction for plasticization (mixing) Before paragraph ⑨, remove part of the solvent

Different from Example 1, the viscous solution entering the plasticizing section is only mixed with a small amount of nitrogen

Mixing, buffer knockout tank at vent

The pressure is controlled to be high while the temperature is low to prevent large amounts of solvent from being evaporated. With the change of raw materials, the composition of the softener is changed to cyclohexane/adipate/naphthenic oil in a weight ratio of 0.1/0.05/0.05. stirring homogenizer After homogenization, use a metering pump Add to reaction softening section

Here the material is cooled to about 50°C. Mixing buffer tank

Cool the jacket with 0°C cold oil to about 5°C, maintain the prepared bromine chloride gas at 7-5°C, and dilute it 10 times with pure nitrogen, and then add the addition amount continuously according to 60%, 30%, and 10%. Pre, middle and post halogenation reaction sections The temperature of the pre-halogenation section is 5-30°C, the temperature of the middle-halogenation section is 50-70°C, and the temperature of the post-halogenation section rises to 70-120°C. Epoxidized soybean oil, 2264, mixed paraffin and cyclohexane, with the quality of rubber as 100, make a solution according to the ratio of 0.5/0.1/0.5/5, and use a metering feeding pump continuously Injection Reaction Stabilizer

in the devolatilization section devolatilizer port Add 5% nitrogen by volume of the halogenated rubber material, maintain the pressure at 3.0-5.0MPa, the pressure at the first exhaust port is about 50KPa, and adjust the temperature at 110-130°C. The pressure at the second exhaust port is about 20KPa, and the temperature is adjusted at 120-150°C to ensure the removal of free halogen and low boiling substances in the halogenated products. In Example 2, the resulting product is bromochlorobutyl rubber, with an output of 34.1kg per hour (containing 8.8% process oil), a product bromine content of 2% by mass, a chlorine content of 0.5% by mass, and a Mooney viscosity of about 42. The heat resistance and color stability of the product are better than monohalogenated products. However, since bromine chloride requires low-temperature preservation, the energy consumption is high and the operation is relatively complicated. However, the present invention has the conditions and methods to overcome this disadvantage, that is, using multi-stage halogenation technology, changing the above-mentioned feeding method, adding chlorine-containing nitrogen in the pre-halogenation stage, so that the polymer contains 0.1-1% chlorine by mass. Adding liquid bromine in the intermediate and post-halogenation reaction sections makes the polymer contain bromine element again, and the amount is in the range of 1-2.5% by mass. The reaction temperature of each section can be increased respectively, and the pre-halogenation section

Chlorine substitution reaction, the temperature is 60 ~ 80 ° C, bromination reaction in the middle halogenation section Reaction temperature 40～60℃, post-halogenation stage

The reaction temperature is 70-110°C. After stabilization and devolatilization, the obtained product has a bromine content of 1.9% by mass, a chlorine content of 0.8%, and a Mooney viscosity of 44. The continuous output can be adjusted in the range of 18-36kg/hour.

Example 3

软化稳定剂按工业己烷/环氧大豆油/石蜡油/己二酸酯比例0.3/0.01/0.1/0.03在搅拌均化釜

混合均匀。用计量泵

加入到反应器软化段在混合缓冲器

中用氯气

与氮气

按体积1/5配成混合气，经增压机

加压后，按40％、30％、20％、10％比例，依次加入前卤化反应段

中卤化反应段

后卤化反应段

和尾卤化反应段，相应温度分别为70～90℃、100～120℃、110～130℃、130～150℃，氯气用量为产品卤素含量的2.04倍。在混合釜

以橡胶质量流率为100，加入5％环己烷

0.05％的1010、0.1％168和0.5％(均为重量)硬脂酸钙

配成溶液，经计量泵

加入反应器稳定段

在脱挥助剂

处，各加入卤化橡胶流率8％和5％氮气，使所含35％(wt)溶剂和氯化氢酸气彻底脱出。脱挥段温度分别控制在110～130℃和120～150℃，相应真空排气机

入口压力可在50～30KPa和10～30KPa范围调控，以保证卤化产品挥发份达到0.2％(wt)以下指标。所获产品氯含量12％(质量)，门尼粘度63左右。产品含11％(wt)的石蜡油和酯，具有十分优良物理性能和加工性，由于硫化速度提高，粘着性大大改善、耐燃性好，与天然橡胶等相容性改善，并可进行共硫化，与非卤化三元乙丙橡胶比，具有更大实用价值和更好综合性能。如果卤化产品需要不含增塑剂时，本卤化反应前软化剂中也可以不加高沸点操作油。而本实施例实现正常卤化橡胶状过程，其产率为25.3kg/h。The closed dry system and screw crushing plasticizer ③ are exactly the same as in Example 1, but the length-to-diameter ratio L/D of the screw extrusion reactor is 66, and a halogenation reaction section at the end of a knot is added. The raw material is dicyclopentadiene-type EPDM rubber with an unsaturation of 2.1% and a Mooney viscosity of 75. The solid EPDM rubber is crushed into irregular blocks with a shape less than 20mm, and the frequency of 30kg is added to the feeding hopper of the screw crushing plasticizer ③ at a frequency of 90 minutes, and nitrogen gas is introduced from ② to remove the air brought in. After ③ crushing and preliminary plasticization, it becomes a small porous floc material, and dry nitrogen is continuously injected at ④ to reversely replace the air entrained by the material. Entering the plasticizing section ⑨ of the halogenation reactor, the material is heated and mixed with pure nitrogen, and the nitrogen containing water and oxygen is decompressed to remove

The softening stabilizer is in the stirring homogenization tank according to the ratio of industrial hexane/epoxy soybean oil/paraffin oil/adipate 0.3/0.01/0.1/0.03

well mixed. with metering pump

Added to the softening section of the reactor in the mixing buffer

Chlorine for medium use

with nitrogen

According to the volume of 1/5 to make a mixture, through a supercharger

After pressurization, according to the proportion of 40%, 30%, 20%, 10%, add the pre-halogenation reaction section in sequence

middle halogenation reaction section

Post-halogenation reaction section

In the tail halogenation reaction section, the corresponding temperatures are 70-90°C, 100-120°C, 110-130°C, and 130-150°C, respectively, and the amount of chlorine gas used is 2.04 times the halogen content of the product. in the mixing kettle

With the mass flow rate of rubber at 100, add 5% cyclohexane

0.05% 1010, 0.1% 168 and 0.5% (all by weight) calcium stearate

Made into a solution, through a metering pump

Added to the reactor stabilization section

in the devolatilizer

At each place, add halogenated rubber at a flow rate of 8% and nitrogen at a rate of 5%, so that 35% (wt) of the solvent and hydrogen chloride acid gas are completely released. Devolatilization section The temperature is controlled at 110-130°C and 120-150°C respectively, and the corresponding vacuum exhauster

The inlet pressure can be adjusted in the range of 50-30KPa and 10-30KPa, so as to ensure that the volatile content of the halogenated product reaches below 0.2% (wt). The obtained product has a chlorine content of 12% (by mass) and a Mooney viscosity of about 63. The product contains 11% (wt) paraffin oil and ester. It has very good physical properties and processability. Due to the increased vulcanization speed, the adhesion is greatly improved, the flame resistance is good, the compatibility with natural rubber is improved, and it can be co-vulcanized. , Compared with non-halogenated EPDM rubber, it has greater practical value and better comprehensive performance. If the halogenated product needs not to contain plasticizer, the softener before the halogenation reaction can also not add high boiling point operating oil. And the present embodiment realizes normal halogenated rubber-like process, and its production rate is 25.3kg/h.

Claims (5)

1. A method for producing halogenated rubber-like polymers, comprising halogenating unsaturated rubber-like polymers with a halogenating agent, characterized in that the whole process is in a closed drying system of a screw and screw extrusion reactor, and the unsaturated rubber The solid polymer and the corresponding additives are continuously and sequentially plasticized or mixed, degassed, softened, multi-stage halogenated, stabilized, devolatilized, metered and cut into pieces, so that the process does not produce waste water and waste gas containing acid and salt. Halogenated rubber-like polymers have controlled halogen content and are free of corrosive acid gases; The unsaturated rubber-like polymer is butyl rubber: unsaturation 0.5-2.5%, Mooney viscosity ML ₁₊₄ , 100°C, 22-60; EPDM rubber, unsaturation 1.2-2.3%, Mooney viscosity ML ₁₊₄ , 100°C, 30-95; or butadiene or isoprene homopolymer or natural rubber rubber-like polymer with unsaturation greater than 15%; The plasticizing or mixing step is a solid unsaturated rubbery polymer or unsaturated rubbery polymer solution with a size of <50mm, which is fully mixed with inert gas in the plasticizing or mixing section for plasticizing or mixing at 70-110°C ; The degassing step is to remove non-condensable gas, moisture, low-boiling point hydrocarbons or unsaturated monomers in the raw material after plasticizing or mixing the material, so that the water and oxygen in the material after degassing Below 20ppm; The softening step is to add a softener to the softening step after degassing, and the amount added is 0.1-1.0 times the weight of the unsaturated rubber-like polymer; The multi-stage halogenation step is in the halogenation section, the material from the softening step is subjected to a multi-stage halogenation reaction with a halogenating agent diluted with a diluent, the halogenation temperature is 0-165°C, and the pressure is 0.2-10MPa; the halogenating agent is chlorine, Hydrogen chloride, bromine chloride gas or liquid bromine, the amount of the halogenating agent is 0.4 to 1.2 times the molar percent of the unsaturated rubber-like polymer; the inert diluent of the halogenating agent is nitrogen or carbon dioxide, and the volume ratio of the halogenating agent to the diluent 1:0.1-30; The stabilization step is to add a stabilizer and an anti-aging agent to the stabilized section of the reactor after halogenation, the amount of the stabilizer added is 0.05-5% by weight of the polymer, and the amount of the anti-aging agent added is 0.05-2% by weight of the polymer; The devolatilization step is to add a devolatilization aid in the devolatilization section of the reactor for devolatilization, remove HCl, N ₂ , a small amount of Cl ₂ and low boiling point substances, and the second-stage devolatilization is: the first-stage devolatilization temperature is 80 -120°C, pressure 30-60KPa, second-stage devolatilization temperature 120-160°C, pressure 20-40KPa; or four-stage devolatilization: The first devolatilization temperature is 60-100°C, the devolatilization pressure is 60-80KPa, The second-stage devolatilization temperature is 100-120°C, the devolatilization pressure is 60-40KPa, The third stage devolatilization temperature is 120-140℃, devolatilization pressure is 40-20KPa, The fourth-stage devolatilization temperature is 140-180°C, and the devolatilization pressure is 10-20KPa; The addition amount of the auxiliary devolatilization agent is 1-20% of the weight of the unsaturated rubbery polymer. 2. The method for producing halogenated rubber-like polymers according to claim 1, characterized in that the inert gas used in the plasticizing section is _N2 , and the plasticizing temperature is 80-100°C; The multi-stage halogenation is three-stage or four-stage halogenation, the amount of halogenating agent added to each stage in the three-stage halogenation is 50%, 30%, and 20% respectively, and the halogenation temperatures are 30-60°C, 60-110°C, 110- 140°C; the amount of halogenating agent added to each stage in the four-stage halogenation is 40%, 30%, 20%, and 10%, respectively, and the halogenation temperature is 0-50°C, 60-100°C, 110-130°C, 130-150°C ℃. 3. The method for producing a halogenated rubber-like polymer according to claim 1, wherein said halogenated rubber-like polymer is: The halogenation reaction temperature of chlorinated butyl rubber is 30-130°C, and the pressure is 0.3-8.0MPa; The halogenation reaction temperature of bromochlorobutyl rubber is 0-120°C, and the pressure is 0.3-5.0MPa; The halogenation reaction temperature of bromobutyl rubber is 10-150°C, and the pressure is 0.3-4.0MPa; Or the halogenation reaction temperature of chlorinated EPDM rubber is 30-140°C, and the pressure is 0.5-6.0MPa. 4. The method for producing a halogenated rubber-like polymer according to claim 1, wherein said halogenated rubber-like polymer is: Chlorinated butyl rubber: its chlorine content is 1.0-1.5% by mass, and its Mooney viscosity is 30-60; Bromobutyl rubber: its bromine content is 1.5-2.5% by mass, and its Mooney viscosity is 22-50; Bromochlorobutyl rubber: the bromine content is 1.0-3.0% by mass, the chlorine content is 0.03-0.8% by mass, and the Mooney viscosity is 22-55; Or chlorinated ethylene-propylene rubber: the chlorine content is 0.8-1.8% by mass or the chlorine content is 13-25% by mass, and the Mooney viscosity is 30-90. 5. The method for producing halogenated rubber-like polymers according to claim 1, characterized in that the helix and screw extrusion reactor is a single helix and screw extrusion reactor with a diameter of Φ60-600 mm and an aspect ratio of L/D 5 ～30, shaft speed 20～300 rpm; Engaging co-rotating twin-screw extrusion reactor, diameter Φ20-250mm, length-to-diameter ratio L/D 25-45, shaft speed 50-500 rpm; Non-meshing/meshing reverse twin-screw extrusion reactor, diameter Φ20-250mm, length-to-diameter ratio L/D40-100, shaft speed 30-500 rpm; Self-cleaning double-helix reactor, diameter Φ50-1000mm, length-to-diameter ratio L/D 5-10, shaft speed 10-100 rpm.

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