CN103224659A - Filler, synthetic rubber and wet rubber compound integrated production method - Google Patents
Filler, synthetic rubber and wet rubber compound integrated production method Download PDFInfo
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Abstract
The invention discloses a filler, synthetic rubber and wet rubber compound integrated production method. A filler is selected from carbon black, white carbon black or a combination of the carbon black and the white carbon black. Compared with traditional and respective independent technologies, the method disclosed in the invention has the advantages of omitting of the post-treatment technologies of the filler and a synthetic rubber, realization of the cycle of sodium carbonate, and full utilization of carbon dioxide and heat generated in a traditional carbon black production technology. So the method can reduce production equipment and simultaneously realize the low carbon and low pollution discharge through the integrated optimization of the process flow in order to reach the recycle purpose.
Description
Technical field
The present invention relates to rubber materials, particularly a kind of filler, synthetic rubber, the integrated production method of wet method rubber unvulcanizate.
Background technology
In the modern rubber industry, the sizing material that manufactures a product contains the fine particle pulverulent filler more than 99%, and their application is the supporting material as rubber on the one hand, improves the physical and mechanical properties and the use properties of improving rubber product of rubber; On the other hand, can give rubber item some special functions again, such as conduction, heat conduction, radiation resistance, magnetic property etc., therefore, filler is only second to rubber itself and occupies second always at the raw-material consumption of rubber item.
The mixing technology of traditional dry method is long owing to its technology mixing time, power consumption is high, dust is many and reason such as dispersed extreme difference makes the mixing technology of its wet method become the research emphasis of more and more enterprises and scientific research institutions, it can not only overcome the mixing shortcoming of dry method, makes the physical and mechanical properties of cross-linked rubber and rubber product quality obtain great improvement simultaneously.
In the mixing technology of wet method, be that filler, the synthetic rubber solution of representative is particularly crucial raw material with carbon black or white carbon black.U.S. Cabot Corporation is as the well-known production of carbon black enterprise in the whole world, its technology is mainly shown in patent CN85101730, CN99809473, major technique is as follows: at first generate fuel gas stream, to guarantee to have enough speed and heat energy, subsequently raw material being injected combustion gases mixes with the high-temp combustion air-flow, rapidly cracking generates carbon black smoke, this flue gas by quench region with termination reaction, with the effluent flow point from and reclaim carbon black product.This technology is the operational path that at present most production of carbon black enterprises adopts, and problem such as fails to make full use of but exist exhaust emissions and a large amount of heat energy.
Disclose among the CN102209586A from the industrial production of carbon compound (such as carbon black, graphite) or from sugared pyrolytic used heat and residual gas and be used to produce electric energy, especially for the operation smelting furnace, and/or used heat is used for endothermic process, but this patent does not have the open carbonic acid gas that produces in the production of carbon black that how to utilize, and reduces emission of carbon-dioxide.
The angry technology of white carbon black is since the sixties in 20th century, and its process characteristic precipitates for add carbonic acid gas in water glass solution, filters and drying, shown in patent GB1040462, GB1088343, US3427130 again.Carbonic acid gas in this technology need be purchased and store, so complicated in the technical process.Along with the development of production technique, it is acidifying substance that the technical characterstic of white carbon black gradually adopts sulfuric acid, shown in patent CA2403954, US5851502, US2002061404, US2003082090, US2007059232, US2008199384.The characteristics of this technology are: after substituting carbonic acid gas with sulfuric acid, the settling rate of white carbon black is accelerated, but could discharge after its byproduct sulfite solution must be handled.
Summary of the invention
At prior art problems, the purpose of this invention is to provide a kind of filler, synthetic rubber, the integrated production method of wet method rubber unvulcanizate.Another object of the present invention provides a kind of rubber unvulcanizate that uses this filler, synthetic rubber, the integrated production method preparation of wet method rubber unvulcanizate.
The advantage of filler of the present invention, synthetic rubber, the integrated production method of wet method rubber unvulcanizate is: 1) integrated carbon black and white carbon black wet method rubber unvulcanizate can be broken through the technical bottleneck of existing elastomeric material, realize the application performance of material, the breakthrough of limiting performance and processing characteristics; 2) more reasonably utilize and distribute four thing amount and energy in the technology, thereby reduce total production cost greatly, by recycle, Sustainable development realizes the product profit maximization; 3) carbon black, white carbon black, rubber effective combination synthetic and rubber unvulcanizate technology can realize the carbonic acid gas low emission, brand-new manufacturing of environmental type robber materials and cooked mode are started in the recycle of waste material and wasted energy.
The invention further relates to following embodiment:
1, a kind of carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
2, a kind of white carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the white carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
3, a kind of carbon black, white carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(3) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(4) production of wet method rubber unvulcanizate: the white carbon black that carbon black that step (1) is obtained and step (2) obtain joins in the synthetic rubber solution that step (3) obtains, obtain mixture by stirring, disperse, condensing, carry out drying behind the desolventizing, be the wet method rubber unvulcanizate.
4, according to the described method of embodiment 1-3, wherein the heat that produced of production of carbon black and exhaust combustion is used for dry white carbon black and wet method rubber unvulcanizate; The production that the carbonic acid gas that production of carbon black and exhaust combustion produce is used for white carbon black replaces mineral acid to react.
5, according to the described method of embodiment 2-3, wherein the yellow soda ash that is produced in the white carbon black production is made in the water glass at white carbon black and is recycled.
6, according to each described method among the embodiment 1-3, wherein the production of wet method rubber unvulcanizate specifically comprises following steps:
Step 1): filler is joined in the rubber solutions, form rubber/filler/solvent mixture by stirring;
Step 2): the rubber/filler in the step 1)/solvent mixture is sent in the knockouts, and in knockouts, contact with one or more fluids in nitrogen, water vapour, water, filler water slurry and the oil and mix the back cohesion, obtain the mixture of rubber/filler compound and solvent;
Step 3): remove solvent and described mixture is carried out drying, obtain rubber/filler wet method rubber unvulcanizate.
7, the solvent that is removed according to embodiment 6 described methods, wherein optional recycling step 3), recycle.
8, according to embodiment 6 described methods, wherein in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, anti-aging agent, coupling agent, promoting agent, antioxidant, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor.
9, according to each described method among the embodiment 1-3, wherein synthetic rubber be ethene, propylene, butylene, amylene, the diene of alkene, heptene, a 4-7 carbon atom or 6-7 carbon atom triolefin or contain the homopolymerization or the copolymerized polymer of the vinyl monomer of other atom or functional group, described other atoms or functional group are Siliciumatom, fluorine atom, chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group; Also comprise the monomeric homopolymerization or the multipolymer that contain above-mentioned atom.
10, according to embodiment 9 described methods, wherein said synthetic rubber is polyhutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
11, a kind of rubber unvulcanizate that uses each method preparation among the embodiment 1-10.
In filler of the present invention, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, when filler was carbon black, production method was specially:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
When filler was white carbon black, production method was specially:
(1) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the white carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
When filler was carbon black and white carbon black, production method was specially:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(3) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(4) production of wet method rubber unvulcanizate: the white carbon black that carbon black that step (1) is obtained and step (2) obtain joins in the synthetic rubber solution that step (3) obtains, obtain mixture by stirring, disperse, condensing, carry out drying behind the desolventizing, be the wet method rubber unvulcanizate.
Method of producing black pigment of the present invention is: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated.
The heat that production of carbon black of the present invention and exhaust combustion are produced can be used for dry white carbon black and wet method rubber unvulcanizate; The carbonic acid gas that production of carbon black and exhaust combustion produce can be used for the production of white carbon black, is used to replace mineral acid to come acidifying service water glass solution.
White carbon black production method of the present invention is: quartz sand and soda ash are at high temperature reacted make service water glass, service water glass water is mixed with solution, the carbonic acid gas that feeds the generation of production of carbon black and exhaust combustion then reacts, precipitation of silica is come out, washing more after filtration,, and utilize the heat that produces in the production of carbon black to carry out drying and make white carbon black, wherein the yellow soda ash that is produced in the white carbon black production is made in the water glass at white carbon black and is recycled.
Synthetic rubber production method of the present invention is: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution.
Described synthetic rubber is for directly obtaining from preparation solution polymerized rubber production line, described solution polymerized rubber is for using ethene, propylene, butylene, amylene, alkene, heptene, the triolefin of the diene of a 4-7 carbon atom or 6-7 carbon atom, or contain the homopolymerization or the copolymerized polymer of the vinyl monomer of other atom or functional group, described other atoms or functional group are Siliciumatom, fluorine atom, the chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group, also comprise and contain above-mentioned monomeric homopolymer and multipolymer, comprising but be not limited to polyhutadiene, polyisoprene; butadiene-styrene rubber; second third glue; butyl rubber; butadiene-acrylonitrile rubber; neoprene latex; silicon rubber; viton; urethanes; chlorosulfonated polyethylene rubber; acrylic elastomer etc.The molecular weight of rubber is 1,000 to 4,000 ten thousand, and is preferred 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.
Wet method rubber unvulcanizate production method of the present invention can comprise the steps:
Step 1): filler is joined in the rubber solutions, form rubber/filler/solvent mixture by stirring;
Step 2): the rubber/filler in the step 1)/solvent mixture is sent in the knockouts, and in knockouts, contact with one or more fluids in nitrogen, water vapour, water, filler water slurry and the oil and mix the back cohesion, obtain the mixture of rubber/filler compound and solvent;
Step 3): remove solvent and described mixture is carried out drying, obtain rubber/filler master batch.
The also optional recycling step 3 that comprises of the method for continuously producing of rubber master batch of the present invention) solvent that is removed is with the step of recycle.In addition, in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, anti-aging agent, coupling agent, promoting agent, antioxidant, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor.
Step 1) in the wet method rubber unvulcanizate production method of the present invention can use method well known in the art to realize.Stirring described in the step 1) can use general stirrer to finish, and includes but not limited to blade mixer, trough mixer, planetary stirring machine, Z-blade mixer etc.
Step 1) in the wet method rubber unvulcanizate production method of the present invention can further include finely divided step, described finely divided can enforcement in the following way: the mixture of above-mentioned stirring gained is sprayed under the situation of high pressure high-shear by a nozzle, to improve the dispersion of filler and/or additive; Make above-mentioned ejecta make mixed solution increase the dispersiveness of filler and/or additive at Guan Zhongyu tube wall bump by swan neck more than; Or make ejecta by a bore repeatedly the pipeline that changes of folding and unfolding come the conversion shear-stress to increase the dispersion of filler and/or additive.Used pressure range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
The formed mixture in described finely divided back can also further improve filler and/or the dispersion of additive in rubber solutions by following smart dispersion:
I. described finely divided mixture is afterwards added in ball mill and/or the colloidal mill continuously and disperse, make filler and/or additive be dispersed in the rubber solutions uniformly;
Ii. described finely divided mixture is afterwards joined continuously and grind in the shredder so that filler and/or additive are well dispersed in the rubber solutions, this shredder has the plane mill of one or more groups high speed rotating and is fixed on the shredder sleeve and fixing pin or the price fixing alternate with the plane mill.
Iii. described finely divided mixture is afterwards joined in the shredder continuously and grind, this shredder has two blades of direction of rotation, described blade has the pore chute, under high pressure can improve filler and/or the degree of scatter of additive in rubber solutions by the blade of rotation.Used pressure range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
Iv. described finely divided mixture is afterwards joined in the multi-layer high-voltage slit dispersion machine continuously, mixture is under high pressure extruded the slit between two-layer, and the strong shearing force that produce this moment can improve filler and/or the degree of scatter of additive in rubber solutions.Used pressure range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
V. described finely divided mixture is afterwards joined in the power decentralized device continuously and disperse, many radially-arranged slits or hole are arranged on the rotor of the high speed rotating of described power decentralized device, mixture with high-speed impact on stator surface so that filler and/or additive be evenly dispersed in the rubber solutions.
In above-mentioned five kinds of finely divided methods two or more use of can connecting mutually.
Solvent in the described rubber solutions is the good solvent of various rubber.Solvent specifically can be aliphatic solvents, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvents includes, but are not limited to all kinds of SOLVENTS gasoline, naphthenic hydrocarbon, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent includes but not limited to benzene,toluene,xylene, vinylbenzene, and described chlorinated hydrocarbon solvent includes but not limited to methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, chlorobenzene, zellon, toluene(mono)chloride.The concentration range of rubber in solution is 1% weight to 60% weight, preferred 5% weight to 40% weight, more preferably 10% weight to 30% weight.
Step 1) in the wet method rubber unvulcanizate production method of the present invention also can add additive simultaneously.Additive can be chosen one or more in the additive that comprises oil, anti-aging agent, coupling agent, promoting agent, antioxidant, thermo-stabilizer, photostabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or promotor wantonly.The consumption of additive therefor is conventional amount used, or adjusts according to practical requirements.
Step 2 in wet method rubber unvulcanizate production method of the present invention) in, rubber/filler in the step 1)/solvent mixture is sent in the knockouts, and in knockouts, contact with one or more fluids in nitrogen, water vapour, filler water slurry and the oil and mix the back cohesion, obtain the mixture of rubber/filler compound and solvent.
Step 2 in the wet method rubber unvulcanizate production method of the present invention) knockouts that uses in can be for having the tubular type knockouts of one or more opening for feed, the feedstock direction of wherein said opening for feed can to condense the axial direction due of organ pipe parallel with tubular type, outlet is in the end of pipe, also can be 1-180 ° of angle with the axial direction due that tubular type is condensed organ pipe, preferably be 20-120 ° of angle, more preferably be 70-100 ° of angle, most preferably be 85-95 ° of angle.When opening for feed when being a plurality of, the feedstock direction of part opening for feed is parallel with the axial direction due of tubular type cohesion organ pipe; The axial direction due of the tube of the feedstock direction of remaining opening for feed and tubular type knockouts is 1-180 ° of angle, preferably be 20-120 ° of angle, more preferably be 70-100 ° of angle, most preferably be 85-95 ° of angle, the feedstock direction of each opening for feed and the vertical cross section of the tubular axis heart on the radial direction that is projected as this cross section to any direction between the tangential direction of this cross section, being preferably radial direction, perhaps is tangential direction.Described opening for feed all is on the axial perpendicular same plane with pipe or described opening for feed is on the different planes.
Step 2 in the wet method rubber unvulcanizate production method of the present invention) knockouts that uses in the knockouts that two or three above mutual concentric pipes are formed of also can serving as reasons, wherein each pipe has one or more opening for feed, the feedstock direction of described opening for feed is to be parallel to the axial direction due of pipe or to be the tangential direction of pipe, and outlet is in the end of pipe.Fluid can directly feed, and also can feed from the tangential direction of tube wall.The end of the opening for feed of each pipe can be in same plane, and also the end of the opening for feed of each pipe the end elongated successively or opening for feed of each pipe from inside to outside shortens successively from inside to outside.
Step 2 in the wet method rubber unvulcanizate production method of the present invention) knockouts that uses in also can be the cartridge type knockouts, and this cartridge type knockouts has only an opening for feed, and this opening for feed is positioned on the upper end or barrel of cartridge type knockouts, and outlet is in the lower end of tube.Fluid can directly inject knockouts by opening for feed, also can inject knockouts with the direction of tangent line along barrel.
Step 2 in the wet method rubber unvulcanizate production method of the present invention) knockouts that uses in can be a tubular as top also, and the bottom is cone shape cone type structure, and has one or more opening for feed.The feedstock direction of opening for feed can be the tangential direction of barrel; Each opening for feed can be in same plane, also can be in Different Plane.The feedstock direction of opening for feed also can be vertical with the axial direction due of tube or be 1-180 ° of angle with the axial direction due of tube, preferred 20-110 ° of angle, more preferably 70-100 ° of angle, 85-95 ° of angle most preferably, the feedstock direction of each opening for feed and the radial direction that is projected as this cross section of the vertical cross section in tube axle center to any direction between the tangential direction of this cross section, be preferably the tangential direction of this cross section.
Step 2 in the wet method rubber unvulcanizate production method of the present invention) rubber/filler/solvent mixture that obtains in one or more fluids in nitrogen, water vapour, filler water slurry and the oil described in and the step 1) enters knockouts by one or more opening for feeds, wherein the temperature of nitrogen is 20-300 ℃, the temperature of water vapour is 100-300 ℃, the temperature of liquid water is 20-100 ℃, the temperature of oil is 20-300 ℃, and the temperature of filler water slurry is 20-100 ℃.Described oil is that rubber materials is made oil-extended rubber oil commonly used.In the step 1) the optional oil that uses can with step 2) in use oily identical or different.The filler that uses in the step 1) can with step 2) in the filler that uses identical or different.
Drying step in the step 3) in the wet method rubber unvulcanizate production method of the present invention is that the heat that utilizes production of carbon black and exhaust combustion to be produced carries out drying.
The method of described recovery solvent can be used any known method in this area, as solvent that will vaporization by surface condensation or directly the method for condensation by contact reclaimed.Refrigerant can adopt water when using the method for direct condensation contact.
Technical scheme of the present invention has following advantage:
In the industrial production in modern times, no matter be that carbon black, white carbon black are the filler manufacturing enterprise of representative, or synthetic rubber and wet method rubber unvulcanizate manufacturing enterprise independently carry out suitability for industrialized production separately.In the production process of single product, exist material and energy is wasted greatly.
In the production of carbon black products, oil fuel or fuel gas is pumped to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated, again by becoming the commercially available prod behind granulation, drying, the finished product packing.Simultaneously, tail gas such as the carbonic acid gas that produces in process of production, nitrogen and a large amount of heats directly discharge atmosphere.
Carbon black production technology has following advantage among the present invention: 1) save post-processing step and equipment such as granulation, drying, finished product packing, reduce production costs; 2) heat of waste heat of Sheng Chaning and exhaust combustion can be used for the production of white carbon black and wet method rubber unvulcanizate, and its heat is made full use of, and reduces production costs; 3) carbonic acid gas in the tail gas is used to produce white carbon black to replace other acidic substance, reduces production costs, and reduces emission of carbon-dioxide; 4) nitrogen in the tail gas can be used for the drying of wet masterbatch, and realizes utilizing again.
In the production of white carbon black, carry out acidifying after quartz sand and soda ash made service water glass, precipitation of silica is come out, more after filtration, washing, dry, roll, be the white carbon black product after granulation and the packing.
The white carbon black production technology has following advantage among the present invention: 1) save roll, post-processing step and equipment such as granulation, packing, reduce production costs; 2) carbonic acid gas that produces in the carbon black process is used for the acidic substance of white carbon black production, reduces production costs, and reduce Carbon emission; 3) the recyclable circulation of byproduct yellow soda ash in the carbon white production process is used for the manufacturing of white carbon black raw water glass, reaches no waste, free of contamination discharging; 4) in white carbon black production, need use a large amount of heats and react drying with white carbon black, thereby being provided by the heat of waste heat that produces in the carbon black process and exhaust combustion, these heats realize making full use of of heat energy.
In elastomeric production process, monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution, postprocessing working procedures such as drying becomes product again.In the technology of the present invention, rubber solutions is directly supplied raw materials for the wet method rubber unvulcanizate, not only save aftertreatment technology and equipment, also improved production efficiency.
In wet method rubber unvulcanizate production process of the present invention, directly use synthetic rubber solution, adopt the filler of not granulation, save the filler pulverizing process, improve the fillers dispersed performance, utilize the heat of production of carbon black and exhaust combustion to carry out drying simultaneously, adopt carbonic acid gas to replace other mineral acids to be used for the acidifying of white carbon black production, reduce emission of carbon-dioxide, again the yellow soda ash that produces is reclaimed the manufacturing that circulation is used for water glass, save the energy, reduce cost.
Therefore, with filler, synthetic rubber, wet method rubber unvulcanizate separately independently production technique compare, the present invention is by four technological process combinations effectively, realize the maximization of the reasonable utilization of breakthrough, the energy and energy consumption of material technology and performance and distribution, social benefit, reach the purpose of low-carbon (LC), low pollution emission and recycle.
Embodiment
Further describe the present invention with embodiment below, but scope of the present invention is not subjected to the restriction of these embodiment.
(1) experimental data is measured with following plant and instrument and measuring method among the embodiment:
The plant and instrument of table 1 rubber sample preparation
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury mixer | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment company limited |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | East, Huzhou, Zhejiang machinery company limited |
The testing method of table 2 vulcanizating glue physical performance and instrument
(2) embodiment and Comparative Examples
Raw material:
Synthetic polyisoprenes rubber, IR-70, her Cohan novel material company limited of Qingdao;
Isoprene, her Cohan novel material company limited of Qingdao;
Oil fuel, Zibo victory flies chemical industry company limited;
White carbon black, H833, Wuxi permanent really silicon industry company limited;
Carbon black, N234, Cabot (China) Investment Co., Ltd;
Zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, company limited is found into by Malaysia;
Anti-aging agent 4020, Flexsys Chemical (M) Sdn Bhd;
Silane coupling agent Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Accelerant CZ, Shandong be Shun's chemical industry company limited still;
Vulkacit D PG, Dan County, Shandong chemical industry company limited;
Sulfur, Lin Yiluo Zhuan Xin Anhua factory;
Comparative Examples 1
In Banbury mixer, 30 parts of white carbon blacks, 30 parts of carbon blacks, 4 parts of silane coupling agent Si69 joined carry out in 100 parts of synthesizing cis polyisoprene mixing, behind filler absorption rubber, add discharging from Banbury mixer in mixing again 2 minutes behind 3.5 parts of zinc oxide, 2 parts of stearic acid, the 2 parts of anti-aging agent 4020, sheet gets premix glue under the roller crossing in the mill then.After parking 8 hours, make rubber unvulcanizate with adding in the premix glue in 2 parts of accelerant CZs, 1 part of vulkacit D PG and the 1.6 parts of Sulfur mills.After descending sheet, parking 8 hours, in 150 ℃ of vulcanizing presses, vulcanize to plateau cure, make dry method cross-linked rubber 1.
Comparative Examples 1 adopts white carbon black, carbon black and the synthetic rubber of directly buying, these raw materials all are independent production, and all comprise follow-up treatment step, as pulverizing drying, packing, storage and transportation etc., the discharging that especially also produces a large amount of tail gas carbon dioxide and heat in the sooty production, the also discharging of by-product in the production of white carbon black, synthetic rubber also comprises subsequent step and equipment such as desolventizing, drying.
Embodiment 1
Oil-fuel pump delivered to main air feed machine provides be preheating to 850 ℃ air through air preheater and mix, burn, produce about 1900 ℃ high-temp combustion air-flow at burning zone; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black of separating being sent in the technology of wet method rubber unvulcanizate, the carbonic acid gas of separating in the tail gas feeds in the production technique of white carbon black, nitrogen feeds in the wet method calendering process, and a large amount of heats of generation use in white carbon black and the mixing operation of wet method.
Carbonic acid gas after tail gas is handled in the production of carbon black is fed the pH value in the service water glass solution of 12.5-13.5, when being reacted to the pH value of solution value and being 8.5-9.0, stop to feed carbon dioxide, more after filtration, wash and utilize the heat drying that produces in the production of carbon black to make white carbon black and deliver in the wet method calendering process.
The isoprene monomer lithium is a catalyzer, and the solution polymerization at intermittence of making solvent with hexane makes polymkeric substance, obtains polyisoprene rubber solution again after removing catalyzer.
In containing 13% polyisoprene rubber solution, carbon black in 30 parts of 100 parts of addings of rubber as above-mentioned production, 30 parts of white carbon blacks as above-mentioned production, 4 parts of silane coupling agent Si69,2 parts of anti-aging agent 4020,3.5 part zinc oxide, 2 parts of stearic acid are sneaked in the isoamyl sol solution, after mixing, under the pressure of 30MPa, be injected in the straight pipe type mixing knockouts of triple feed inlet through an inlet, the 0.5MPa water vapor that production of carbon black tail gas boiler is produced feeds in the knockouts by two other inlet simultaneously, the gained mixture sprays into moisture eliminator by a jet exit of knockouts, this moisture eliminator utilizes the heat that produces in the production of carbon black to carry out drying, form the solid powdery material, be master batch 1 more after drying.
Master batch 1 behind bag roller in the mill, is added sheet under 2 parts of accelerant CZs, 1 part of vulkacit D PG and the 1.6 parts of Sulfur thin-passes, park 8 hours after, in 150 ℃ vulcanizing press, vulcanize to plateau cure, make wet method cross-linked rubber 1.
Comparative Examples 2
In Banbury mixer, 3.5 parts of zinc oxide, 2 parts of stearic acid, 4020,55 parts of carbon blacks of 2 parts of anti-aging agent are joined carry out in 100 parts of synthesizing cis polyisoprene mixing, discharging from Banbury mixer in mixing 2 minutes, sheet gets premix glue under the roller crossing in the mill then.After parking 8 hours, 1.3 parts of accelerant CZs and 1.2 parts of Sulfurs are added in the premix glue in mill make rubber unvulcanizate.After descending sheet, parking 8 hours, in 150 ℃ of vulcanizing presses, vulcanize to plateau cure, make dry method cross-linked rubber 2.
Comparative Examples 2 adopts carbon black and the synthetic rubber of directly buying, these raw materials all are independent production, and all comprise follow-up treatment step, as pulverizing drying, packing, storage and transportation etc., especially also produce the discharging of a large amount of tail gas carbon dioxide and heat in the sooty production, synthetic rubber also comprises subsequent step and equipment such as desolventizing, drying.
Embodiment 2
Oil-fuel pump delivered to main air feed machine provides be preheating to 850 ℃ air through air preheater and mix, burn, produce about 1900 ℃ high-temp combustion air-flow at burning zone; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black of separating being used for the technology of wet method rubber unvulcanizate, burn in the tail gas boiler carbonic acid gas produced of tail gas is used for the production technique of white carbon black, and the heat of generation uses in white carbon black and the mixing operation of wet method.
The isoprene monomer lithium is a catalyzer, and the solution polymerization at intermittence of making solvent with hexane makes polymkeric substance, obtains polyisoprene rubber solution again after removing catalyzer.
In containing 13% polyisoprene rubber solution, carbon black in 55 parts of 100 parts of addings of rubber as above-mentioned production, 2 parts of anti-aging agent 4020,3.5 part zinc oxide, 2 parts of stearic acid are sneaked in the isoamyl sol solution, after mixing, under the pressure of 30MPa, be injected in the straight pipe type mixing knockouts of triple feed inlet through an inlet, the 0.5MPa water vapor that the carbon black tail gas boiler is produced feeds in the knockouts by two other inlet simultaneously, the gained mixture sprays into moisture eliminator by a jet exit of knockouts, this moisture eliminator utilizes the heat that produces in the production of carbon black to carry out drying, form the solid powdery material, be master batch 2 more after drying.
Master batch 2 behind bag roller in the mill, is added behind 1.3 doses of CZ and 1.2 Sulfurs sheet under the thin-pass, park 8 hours after, on 150 ℃ vulcanizing press, vulcanize to plateau cure, make wet method cross-linked rubber 2.
Table 3 is wet, the physicals of dry method cross-linked rubber
Table 3 is the physicals of the resulting cross-linked rubber of Comparative Examples of the embodiment of wet masterbatch under different ingredients and technology and dry method rubber unvulcanizate.Therefrom as can be seen, under same recipe, wet masterbatch is compared with maskerbatch of dry process, the dispersiveness of filler in rubber improves greatly, and the hardness of cross-linked rubber is lower, and tensile strength and tensile yield are higher, the elasticity height, dynamic compression is given birth to hot low, and wear resisting property is better.Simultaneously, in the preparation process of wet method rubber unvulcanizate, carbon black, white carbon black, synthetic rubber all save post-processing step as main raw material, and heat and the carbonic acid gas that is produced in the carbon black process made full use of, save a large amount of energy and consumption of raw materials, reduce production cost, and realized the zero release of carbonic acid gas.
Claims (11)
1. a carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
2. a white carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(2) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(3) production of wet method rubber unvulcanizate: the white carbon black that step (1) is obtained joins in the synthetic rubber solution that step (2) obtains, by stir, disperse, cohesion obtains mixture, carries out drying behind the desolventizing, is the wet method rubber unvulcanizate.
3. a carbon black, white carbon black, synthetic rubber, the integrated production method of wet method rubber unvulcanizate, it comprises the steps:
(1) sooty production: oil fuel or fuel gas is delivered to main air feed machine provides the air that is preheating under the certain temperature through air preheater are mixed, burn at burning zone, produce the high-temp combustion air-flow; Stock oil sprays into Reaktionsofen trunnion section after preheater is preheated to certain temperature, mix with the high-temp combustion air-flow, and carbon black smoke is produced in cracking rapidly; Then, spray into quenched water, reduce flue-gas temperature and make reaction terminating, by behind the bag filter carbon black being separated;
(2) production of white carbon black: quartz sand and soda ash at high temperature reacted make service water glass, service water glass water is mixed with solution, add mineral acid then and react, precipitation of silica is come out, more after filtration, washing, drying make white carbon black;
(3) elastomeric production: monomer in solvent under the effect of catalyzer polymerization make polymkeric substance, and then after removing catalyzer, obtain synthetic rubber solution;
(4) production of wet method rubber unvulcanizate: the white carbon black that carbon black that step (1) is obtained and step (2) obtain joins in the synthetic rubber solution that step (3) obtains, obtain mixture by stirring, disperse, condensing, carry out drying behind the desolventizing, be the wet method rubber unvulcanizate.
4. according to the described method of claim 1-3, wherein the heat that is produced in production of carbon black and the exhaust combustion is used for dry white carbon black and wet method rubber unvulcanizate; The production that the carbonic acid gas that production of carbon black and exhaust combustion produced is used for white carbon black replaces mineral acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc. to react.
5. according to the described method of claim 2-3, wherein the yellow soda ash that is produced in the white carbon black production is made in the water glass at white carbon black and is recycled.
6. according to each described method among the claim 1-3, wherein the production of wet method rubber unvulcanizate specifically comprises following steps:
Step 1): filler is joined in the rubber solutions, form rubber/filler/solvent mixture by stirring;
Step 2): the rubber/filler in the step 1)/solvent mixture is sent in the knockouts, and in knockouts, contact with one or more fluids in nitrogen, water vapour, water, filler water slurry and the oil and mix the back cohesion, obtain the mixture of rubber/filler compound and solvent;
Step 3): remove solvent and described mixture is carried out drying, obtain rubber/filler wet method rubber unvulcanizate.
7. the solvent that is removed method according to claim 6, wherein optional recycling step 3), recycle.
8. method according to claim 6 is wherein in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, anti-aging agent, coupling agent, promoting agent, antioxidant, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor.
9. according to each described method among the claim 1-3, wherein synthetic rubber be ethene, propylene, butylene, amylene, the diene of alkene, heptene, a 4-7 carbon atom or 6-7 carbon atom triolefin or contain the homopolymerization or the copolymerized polymer of the vinyl monomer of other atom or functional group, described other atoms or functional group are Siliciumatom, fluorine atom, chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group; Also comprise the monomeric homopolymerization or the multipolymer that contain above-mentioned atom.
10. method according to claim 9, wherein said synthetic rubber are polyhutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
11. rubber unvulcanizate that uses each method preparation among the claim 1-10.
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| CN103419291A (en) * | 2013-08-05 | 2013-12-04 | 怡维怡材料研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby |
| CN104311929A (en) * | 2014-11-03 | 2015-01-28 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in sedan tire tread rubber |
| CN104341686A (en) * | 2014-11-03 | 2015-02-11 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch to car tire inner liner rubber |
| CN105745257A (en) * | 2013-11-11 | 2016-07-06 | 东洋橡胶工业株式会社 | Rubber composition |
| CN106185951A (en) * | 2016-06-30 | 2016-12-07 | 安徽省含山县锦华氧化锌厂 | A kind of white carbon and preparation method thereof |
| CN108997795A (en) * | 2018-07-10 | 2018-12-14 | 丰城黑豹炭黑有限公司 | A kind of carbon black materials and preparation process |
| CN110193890A (en) * | 2019-06-06 | 2019-09-03 | 益凯新材料有限公司 | A kind of wet process mixing continuous production technology of isoprene rubber |
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| CN103419291A (en) * | 2013-08-05 | 2013-12-04 | 怡维怡材料研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby |
| CN103419291B (en) * | 2013-08-05 | 2016-04-27 | 怡维怡橡胶研究院有限公司 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
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| CN104311929A (en) * | 2014-11-03 | 2015-01-28 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in sedan tire tread rubber |
| CN104341686A (en) * | 2014-11-03 | 2015-02-11 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch to car tire inner liner rubber |
| CN106185951A (en) * | 2016-06-30 | 2016-12-07 | 安徽省含山县锦华氧化锌厂 | A kind of white carbon and preparation method thereof |
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| CN110193890B (en) * | 2019-06-06 | 2020-05-19 | 益凯新材料有限公司 | Wet mixing continuous production method of isoprene rubber |
| CN113502070A (en) * | 2021-08-04 | 2021-10-15 | 烁元新材料(东营)股份有限公司 | Low-rolling-resistance carbon black discharging forming device for tire and forming processing method |
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