CN111944076B - Water washing process of halogenated butyl rubber - Google Patents
Water washing process of halogenated butyl rubber Download PDFInfo
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- CN111944076B CN111944076B CN202010921951.8A CN202010921951A CN111944076B CN 111944076 B CN111944076 B CN 111944076B CN 202010921951 A CN202010921951 A CN 202010921951A CN 111944076 B CN111944076 B CN 111944076B
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Abstract
The invention discloses a water washing process of halogenated butyl rubber, which comprises the following steps: adding alkali liquor and first washing water into halogenated glue solution containing hydrogen halide to obtain a first mixed system; standing and separating the first mixed system to obtain a first water phase system and a first gel phase system; the first water phase system enters a wastewater treatment process; adding second washing water into the first gel phase system to obtain a second mixed system; standing and separating the second mixed system to obtain a second water phase system and a second gel phase system; the second water phase system enters a wastewater treatment process; adding an auxiliary agent into the second gel phase system to obtain a third mixed system; adding third washing water and hot steam into the third mixed system to carry out flash evaporation to remove the organic solvent; then dewatering and drying to obtain the waste water and the finished product of halogenated butyl rubber; the removal wastewater is recycled as the first wash water, the second wash water and the third wash water. The invention can effectively reduce the content of halogen salt in rubber and realize the recycling of waste water.
Description
Technical Field
The invention relates to the technical field of halogenated butyl rubber, in particular to a water washing process of halogenated butyl rubber.
Background
The butyl rubber has excellent air tightness and aging resistance, and is widely applied to tire inner tubes, vulcanization capsules, airtight sealing materials, anticorrosion and waterproof materials, medical materials and the like. However, butyl rubber is deficient in cure rate, compatibility with other highly unsaturated rubbers, and adhesion to metals, which in turn affects its processing applications. After the butyl rubber is halogenated, the activity of double bonds in the butyl rubber molecules can be enhanced, so that the vulcanization speed of the halogenated butyl rubber is accelerated, the compatibility with other rubbers with high unsaturation degree is increased, the halogenated butyl rubber can be co-vulcanized, the adhesion with metal is obviously improved, and the halogenated butyl rubber is more suitable for preparing an inner liner of a tire.
Currently, the finished halogenated butyl rubber is prepared by reacting butyl rubber with halogen (chlorine or liquid bromine), and a large amount of halogen-containing acid (HCl or HBr) is generated after the reaction, and a large amount of halogen salt is generated after the reaction is neutralized by alkali (NaOH or other alkali solution). The current conventional production process comprises the following units: preparing a basic glue solution, halogenating butyl rubber, adding an alkali liquor to neutralize, stripping to remove a solvent, and drying to perform post-treatment, wherein the production process comprises the steps of discharging sewage with the chloride ion content of 0.2-0.3 wt% (in chlorinated rubber production), discharging sewage with the bromide ion content of 0.5-0.9 wt% (in brominated rubber production), and finally obtaining chlorinated butyl rubber with the halide salt residual NaCl (NaOH neutralized) of 50-200 ppm, brominated butyl rubber with the halide salt residual NaBr of 250-400 ppm and a finished halogenated butyl rubber with the salt content higher than that of the halogenated butyl rubber. The residual salt can form blooming on the surface of the product to influence the viscosity of the rubber product, and further crystallization of salt with high local salt content can occur, so that the air tightness of the rubber product is influenced. In conclusion, the high content of halogen salt can adversely affect the processing and use of rubber products and affect the product quality, so that the halogen salt residue in the rubber needs to be reduced through process improvement.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a water washing process of halogenated butyl rubber.
In order to solve the problems, the invention adopts the following technical scheme:
a water washing process of halogenated butyl rubber comprises the following steps:
adding alkali liquor and first washing water into halogenated glue solution containing hydrogen halide to obtain a first mixed system;
standing and separating the first mixed system to obtain a first water phase system and a first gel phase system; the first water phase system enters a wastewater treatment process;
adding second washing water into the first gel phase system to obtain a second mixed system;
standing and separating the second mixed system to obtain a second water phase system and a second gel phase system; the second water phase system enters a wastewater treatment process;
adding an auxiliary agent into the second gel phase system to obtain a third mixed system;
adding third washing water and hot steam into the third mixed system to carry out flash evaporation to remove the organic solvent;
then dewatering and drying to obtain the waste water and the finished product of halogenated butyl rubber;
the removal waste water is recycled to be used as the first wash water, the second wash water, and the third wash water.
Preferably, the method further comprises the step of adding a surfactant to the first mixed system and the second mixed system, wherein the surfactant is an alkyl ester emulsifier or a polyol ester emulsifier.
Preferably, the method further comprises the following steps: and heating and devolatilizing the first aqueous phase system and the second aqueous phase system by using the removed organic solvent so as to remove organic matters in the first aqueous phase system and the second aqueous phase system.
Preferably, the pH value of the first mixed system is 8.0-10.0, and the addition amount of the surfactant accounts for 0.01-0.05% of the mass of the first mixed system.
Preferably, the mass ratio of the first rubber phase system to the first water phase system in the first mixed system is (2.0-7.0): 1.
Preferably, the mass ratio of the second rubber phase system to the second water phase system in the second mixed system is (2.0-7.0): 1.
Preferably, the mixing process of the first mixing system and the second mixing system is carried out in an axial-flow guide cylinder type mixer.
Preferably, the water content in the first gel phase system is 5.0-8.0 wt%, and the water content in the second gel phase system is 5.0-8.0 wt%.
Preferably, the content of the halogen ions in the first aqueous phase system is 0.6-2.0 wt%.
Preferably, the content of halogen salt in the finished halogenated butyl rubber is 30-100 ppm.
Compared with the prior art, the invention has the technical effects that:
the water washing process of the halogenated butyl rubber can effectively reduce the residual quantity of halogen salt in the finished halogenated butyl rubber, and the first washing water, the second washing water and the third washing water used in the water washing process of the halogenated butyl rubber come from the circulating removal wastewater during dehydration treatment, namely the water washing process of the invention realizes the recycling of the removal wastewater, on one hand, the consumption of fresh water in the water washing process of the halogenated butyl rubber can be effectively reduced, on the other hand, the wastewater quantity discharged in the water washing process of the halogenated butyl rubber can be reduced, and the use cost of fresh water and the wastewater treatment cost are reduced.
Drawings
FIG. 1 is a process flow diagram of a water washing process for halogenated butyl rubber according to an embodiment of the present invention.
In the figure, 1, a first axial flow guide cylinder type mixer, 2, a first liquid separation tank, 3, a second axial flow guide cylinder type mixer, 4, a second liquid separation tank, 5, an auxiliary agent mixing tank, 6, a condensation kettle, 7, vibration dewatering equipment, 8, extrusion dewatering equipment, 9, a high-concentration sewage buffer storage tank, 10, a low-concentration sewage buffer storage tank, 11 and falling film evaporation equipment.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The embodiment of the invention provides a water washing process of halogenated butyl rubber, a process flow chart is shown in figure 1, and the water washing process comprises the following steps:
(1) adding alkali liquor and first washing water into halogenated glue solution containing hydrogen halide to obtain a first mixed system;
(2) standing and separating the first mixed system to obtain a first water phase system and a first gel phase system; the first water phase system enters a wastewater treatment process;
(3) adding second washing water into the first gel phase system to obtain a second mixed system;
(4) standing and separating the second mixed system to obtain a second water phase system and a second gel phase system; the second water phase system enters a wastewater treatment process;
(5) adding an auxiliary agent into the second gel phase system to obtain a third mixed system;
(6) adding third washing water and hot steam into the third mixed system to carry out flash evaporation to remove the organic solvent;
(7) then dewatering and drying to obtain the waste water and the finished product of halogenated butyl rubber; the removal wastewater is recycled as the first wash water, the second wash water and the third wash water.
In addition, in the process of washing the halogenated rubber solution, because the mutual solubility of the alkaline aqueous solution and the high-viscosity halogenated butyl rubber solution is poor, the mass transfer between the aqueous phase and the oil phase is difficult, the washing process of the halogenated butyl rubber can also comprise the following steps:
(8) and adding a surfactant into the first mixed system and the second mixed system, wherein the surfactant is an alkyl ester emulsifier or a polyol ester emulsifier. The surfactant is added into the mixed system, so that the surface tension of the water phase is reduced, the water phase and the high-viscosity glue phase are fully mixed and transferred, and the washing effect is further improved. Alkyl ester emulsifiers can be alkyl methacrylate emulsifiers or potassium cetyl phosphate, and potassium cetyl phosphate is preferably used in the present embodiment. The polyol ester emulsifier can be glyceryl monostearate, fatty acid sorbates or polysorbates, and Tween-80 is preferably used in the embodiment of the invention. Preferably, the addition amount of the surfactant accounts for 0.01-0.05% of the mass of the first mixed system; the addition amount of the surfactant accounts for 0.01-0.03% of the mass of the second mixed system.
On the other hand, the first aqueous phase system and the second aqueous phase system are not beneficial to discharge of sewage because 300-500 ppm of organic solvent hexane is usually dissolved in the sewage; on the other hand, the temperature of the organic solvent hexane gas recovered by flash evaporation removal is as high as 80-95 ℃, so that the embodiment of the invention further comprises the following steps:
(9) and heating and devolatilizing the organic matters in the sewage of the first water phase system and the second water phase system by using the removed high-temperature gaseous organic solvent so as to reduce the content of the organic matters in the sewage and improve the discharge quality of the sewage.
The halogenated rubber solution containing the hydrogen halide in the step (1) is a mixed solution obtained by dissolving butyl rubber in an organic solvent to enable the concentration of the butyl rubber contained in the organic solvent to be 14-20 wt%, and then adding a halogenating reagent to carry out halogenation reaction. The following organic solvents can be generally used: alkane, halogen-containing alkane, aromatic hydrocarbon, halogen-containing aromatic hydrocarbon, and derivatives or mixtures thereof, and hexane is preferably used as a solvent for dissolving the butyl rubber in this embodiment. The halogenating agent comprises a chlorinating agent and a brominating agent, the chlorinating agent can be selected from chlorine, sulfuryl chloride, iodine monochloride and the like, and chlorine is preferably used as the chlorinating agent in the embodiment; the brominating agent can be selected from bromine water, liquid bromine, sulfuryl bromide, etc., and in this embodiment, liquid bromine is preferably used as the brominating agent.
Since the halogenation reaction is a substitution reaction, eachReaction of 1 mol halogen (Br) 2 /Cl 2 ) Molecules can generate 1 mol of hydrogen halide (HBr/HCl), the halogenation reaction speed is very high, and if the hydrogen halide generated by the halogenation reaction cannot be neutralized quickly in time, the hydrogen halide can be gathered in the glue solution, and the glue solution is strongly acidic. Under strong acidic condition, the molecular structure of the halogenated butyl rubber is rearranged, and secondary substitution is transferred to primary substitution. Because the reaction speed of primary bromine is higher than that of secondary bromine in the vulcanization process, the rubber vulcanization time is easy to be uncontrolled if a large amount of primary bromine exists in the brominated butyl rubber, and the problem of scorching and the like are caused due to the higher vulcanization speed. Therefore, in order to ensure the quality of the halogenated butyl rubber product, alkali liquor needs to be added into the reaction product after the halogenation reaction for rapid and sufficient neutralization. Common alkali solution comprises NaOH, KOH, Ca (OH) 2 Etc., NaOH is preferably used in this embodiment.
The neutralization process of the glue solution is a reaction process which needs mass transfer between two phases of oil and water, and is a process that hydrogen halide in the glue solution enters a water phase through mass transfer and then reacts with NaOH to form NaBr/NaCl. The neutralization reaction process, i.e., the mixing process of the first mixing system, is usually carried out in a vessel with a stirring device, and the mass transfer is enhanced by stirring. Preferably, the mixing process of the first mixing system of the embodiment is performed in a first axial flow guide drum mixer, the first axial flow guide drum mixer is innovatively used as a neutralization reaction device in the embodiment, the halogenated glue solution is introduced into the reactor, meanwhile, the alkali solution and the first recycled washing water are introduced, the mass ratio of the first glue phase system to the first water phase system in the first mixing system is controlled to be (2.0-7.0): 1, preferably (2.0-6.0): 1, and the glue phase system and the water phase system can be better separated under the condition of controlling the washing water consumption by controlling the quality of the glue phase system and the water phase system.
For a two-phase mixing traditional process, a strong shear stirrer is usually used as mixing equipment, and strong shear force is used for ensuring full mixing mass transfer, but high-speed shear force in the mixing process can damage the molecular structure of halogenated butyl rubber and even break the molecular chain of rubber, so that the quality of rubber products is influenced. While stirring in the processThe invention creatively uses a first axial flow guide cylinder type mixer stirring device in the halogenated butyl rubber washing process, and guarantees the mass transfer effect by high-speed rotation and rapid and multiple circulation along the guide cylinder. For shearing stirring, axial compressor water conservancy diversion cylinder mixer agitated vessel can effectually get rid of the stirring blind spot, and the mass transfer homogeneity is better, mixes mass transfer efficiency and is higher, under the prerequisite of guaranteeing rubber product quality, can further improve the washing effect, and equipment power is lower relatively simultaneously, more energy saving and consumption reduction. After neutralization, standing and separating, wherein the content of halogen ions in the first water phase system is 0.6-2.0 wt%, and Br - 1.0 to 2.0wt% (brominated), Cl - The content of (chloridization) is 0.6-1.5 wt%, and in order to ensure the neutralization effect and inhibit the emulsification phenomenon, the pH value of the first mixed system is controlled to be 8.0-10.0.
And (3) standing and separating for 20-50 min in the step (2), wherein the water content in the first gel phase system obtained after separation is 5.0-8.0 wt%. Compared with the conventional production process, the concentration of the halogen ions in the first aqueous phase system is increased to 1.0-2.0 wt%, the total amount of the halogen ions in the high-concentration wastewater accounts for more than 90% of the discharge amount of the halogen ions in the whole production process, and the increase of the concentration of the halogen ions in the first aqueous phase system is beneficial to the improvement of the subsequent recovery efficiency of the halogen ions and the reduction of the recovery energy consumption.
In the step (3), the mass ratio of the second rubber phase system to the second water phase system in the second mixed system is (2.0-7.0): 1, and preferably (3.0-6.0): 1. By controlling the quality of the gel phase system and the water phase system, the gel phase system and the water phase system can be better separated under the condition of controlling the dosage of washing water.
And (4) standing and separating for 20-50 min, wherein the water content in the second gel phase system obtained after separation is 5.0-8.0 wt%. Preferably, the mixing process of the second mixing system is carried out in a second axial flow guided bowl mixer. The full water washing is realized through an axial flow guide cylinder type mixer, and the halogen ion content Br in the second water phase system after the water washing - 5000-8000 ppm (brominated), Cl - The content of (chlorinated) is 2000-5000 ppm.
The addition of the auxiliary agent in the step (5) is to better disperse the halogenated butyl rubber glue solution and prevent the subsequent halogenated butyl rubber product from being degraded by high temperature in the drying process to cause the quality reduction of the product. The added auxiliary agents include but are not limited to rubber antioxidant, dispersant and stabilizer.
And (3) carrying out flash evaporation in a condensation kettle in the step (6), adding steam and circulating third washing water, removing and recovering hexane serving as an organic solvent, forming halogenated butyl rubber into particles and dispersing the particles in circulating hot water to form colloidal particle water, wherein the content of halogen ions in the water phase is reduced to below 300ppm due to dilution of incremental water brought by the steam and the like and the circulating third washing water, and the pH value of a water system is 7.0-10.0.
And (4) dehydrating in the step (7) in a vibration dehydrating screen and an extrusion dehydrating machine respectively, dehydrating to remove most of water in the glue solution, and allowing trace water to enter subsequent drying equipment along with the rubber for further drying. The content of halogen salt (NaCl or NaBr) in the final butyl rubber product can be reduced to 30-100 ppm, and the quality of halogenated butyl rubber is guaranteed. The wastewater removed is recycled as circulating hot water in a halogenation device and enters a first axial flow guide flow cylinder mixer, a second axial flow guide flow cylinder mixer and a condensation kettle. The incremental water entering the system is mainly low-pressure steam, alkali liquor, water brought by an auxiliary agent and possibly machine seal water, all salt-containing sewage is discharged through a wastewater treatment process, and in order to maintain the water quantity balance of the system, the water quantity (influencing the external discharge capacity) entering the first axial flow guide flow cylinder type mixer and the second axial flow guide flow cylinder type mixer is adjusted according to the actual incremental water condition of the device, so that the balance between the external salt-containing sewage quantity and the system incremental water quantity is achieved.
The measurement of the halogen ions was performed using an X-ray fluorescence spectrometer.
The water washing process of the halogenated butyl rubber can effectively reduce the residual quantity of halogen salt in the finished halogenated butyl rubber, and the first washing water, the second washing water and the third washing water used in the water washing process of the halogenated butyl rubber come from the circulating removal wastewater during dehydration treatment, namely the water washing process of the invention realizes the recycling of the removal wastewater, on one hand, the consumption of fresh water in the water washing process of the halogenated butyl rubber can be effectively reduced, on the other hand, the wastewater quantity discharged in the water washing process of the halogenated butyl rubber can be reduced, and the use cost of fresh water and the wastewater treatment cost are reduced. According to the invention, the first axial flow guide cylinder type mixer and the second axial flow guide cylinder type mixer are innovatively used for strengthening the mass transfer process, the retention time of materials in the first axial flow guide cylinder type mixer and the second axial flow guide cylinder type mixer is 0.5-5 min, the materials are quickly and fully mixed for mass transfer, so that the reaction is quicker, the halogen ion content in the first water phase system and the second water phase system after standing separation is higher, the halogen ion content remained in the halogenated butyl rubber product is lower, the wastewater treatment cost can be reduced, and the product quality of the halogenated butyl rubber can be improved.
The water washing process of halogenated butyl rubber of the embodiment of the invention is carried out in a water washing system, the process flow is shown in figure 1, and the water washing system comprises a first axial flow guide cylinder type mixer 1, a first liquid separation tank 2, a second axial flow guide cylinder type mixer 3, a second liquid separation tank 4, an auxiliary agent mixing tank 5, a condensation kettle 6, a vibration dehydration device 7, an extrusion dehydration device 8, a high-concentration sewage buffer storage tank 9, a low-concentration sewage buffer storage tank 10 and a falling-film evaporator 11. Specifically, a halogenated glue solution with a mass concentration of 14-20 wt%, an alkali solution and circulating hot water (first washing water) are added into a first axial flow guide drum type mixer 1, and the mass ratio of the glue solution phase to the water phase is controlled to be 2.0-7.0, preferably 2.0-6.0. The neutralized first mixed system enters a first liquid separation tank 2 for standing and liquid separation, a baffle is arranged in the first liquid separation tank 2, the density of the glue phase is about 0.7 due to the fact that the density of the glue phase is light, the first glue phase system enters the glue solution side through the baffle after standing and is extracted, and the first water phase system is discharged to a high-concentration sewage buffer storage tank 8 from the bottom. The first liquid separation tank 2 is large in volume, and the residence time of the glue solution in the tank is 20-50 min. And (3) introducing the first glue phase system after liquid separation into a second axial flow guide drum type mixer 3 for washing, introducing a large amount of circulating hot water (second washing water) for washing, wherein the mass ratio of the glue phase to the introduced water phase is 2.0-7.0, and preferably 3.0-6.0. And (3) introducing the second mixed system after the washing into a second liquid separation tank 4 for standing and liquid separation, wherein the residence time of the glue solution in the tank is 20-50 min. And discharging the obtained second water phase system from the bottom to a low-concentration sewage buffer storage tank 10, and adding the second glue phase system into an auxiliary agent mixing tank 5 to add an auxiliary agent. And then introducing the glue solution into a condensation kettle 6, adding low-pressure steam and circulating hot water (third washing water), removing and recovering a solvent hexane, forming rubber into particles and dispersing the rubber particles in the circulating hot water to form colloidal particle water, removing most of water in the glue from the colloidal particle water in a vibration dehydration device 7 and an extrusion dehydration device 8 respectively, and further drying the trace water in a subsequent drying device along with the rubber. The removed wastewater is recycled as circulating hot water in a halogenation device and enters a first axial flow guide flow cylinder mixer 1, a second axial flow guide flow cylinder mixer 3 and a condensation kettle 6.
In addition, 300-500 ppm of organic solvent hexane is usually dissolved in the sewage in the high-concentration sewage buffer storage tank 8 and the low-concentration sewage buffer storage tank 10, which is not beneficial to sewage discharge; on the other hand, the temperature of the solvent hexane gas removed and recovered by the coagulation kettle 6 is as high as 80-95 ℃, so that the embodiment of the invention further utilizes the high-temperature hexane gas removed by the coagulation kettle 6 to heat and devolatilize the organic hexane in the sewage, so as to reduce the hexane content in the sewage and improve the discharge quality of the sewage. Specifically, the solvent hexane gas removed and recovered by the condensation kettle 6, the sewage in the high-concentration sewage buffer storage tank 8 and the low-concentration sewage buffer storage tank 10 are introduced into the falling-film evaporator 11, the temperature of the sewage can be increased to 75-90 ℃ after heat exchange is carried out by the falling-film evaporator 11, and the hexane content in the sewage can be further reduced to below 50 ppm.
The following is a further description with reference to specific examples.
Example 1
Adding 16.8wt% of glue solution containing brominated butyl rubber into a first axial flow guide cylinder type mixer, then adding 40mmol/L of sodium hydroxide solution and circulating hot water, controlling the pH of a mixed system to be 8.0-8.5, wherein the mass ratio of a glue phase to a water phase in the mixed system is 3:1, and transferring the mixed system into a first liquid separation tank after the mixed system stays in the first axial flow guide cylinder type mixer for 3 min; standing and separating in a first liquid separation tank for 30min, transferring the gel phase into a second axial flow guide cylinder type mixer, and discharging the water phase into a high-concentration sewage buffer storage tank; simultaneously introducing circulating hot water into the second axial flow guide cylinder type mixer, controlling the mass ratio of a gel phase to a water phase in a mixed system to be 3:1, and transferring the mixed system into a second liquid separation tank after the mixed system stays in the second axial flow guide cylinder type mixer for 3 min; standing and separating in a second liquid separation tank for 30min, transferring the gel phase into an auxiliary agent mixing tank, and discharging the water phase into a low-concentration sewage buffer storage tank; after adding related auxiliary agents, transferring the gel phase into a condensation kettle, introducing low-pressure steam and circulating hot water, and discharging solvent hexane through flash evaporation; and then dehydrating and drying the rubber phase to obtain the finished product of brominated butyl rubber. Introducing the solvent hexane gas removed and recovered by the condensation kettle, the high-concentration sewage buffer storage tank and the sewage in the low-concentration sewage buffer storage tank into a falling-film evaporator, wherein the temperature of the sewage can be increased to 85 ℃ after heat exchange by the falling-film evaporator, and the hexane content in the sewage can be reduced to 43 ppm.
Example 2
The difference from the embodiment 1 is that the pH of a mixing system in a first axial flow guide cylinder type mixer is controlled to be 9.0-10.0, and the mass ratio of a gel phase to a water phase in the mixing system is 5: 1; the mass ratio of the gel phase to the water phase in the second axial flow guide drum mixer is 6: 1.
Example 3
The difference from the embodiment 1 is that the pH of a mixing system in a first axial flow guide cylinder type mixer is controlled to be 8.5-9.0, and the mass ratio of a gel phase to a water phase in the mixing system is 6: 1; the mass ratio of the gel phase to the water phase in the second axial flow guide drum mixer is 5: 1.
Example 4
The difference from the embodiment 1 is that the concentration of the brominated butyl rubber in the brominated rubber solution is 19.6wt%, and the retention time of the mixed system in the first liquid separation tank and the second liquid separation tank is 50 min; in a first axial flow guide drum type mixer, the mass ratio of a gel phase to a water phase in a mixing system is 2: 1; in the second axial flow induced flow drum mixer, the mass ratio of the gum phase to the aqueous phase was 2: 1.
Example 5
It differs from example 1 in that a dope containing 14.2% by weight of chlorinated butyl rubber was added to the first axial flow guiding drum mixer.
Example 6
It differs from example 1 in that a dope containing chlorinated butyl rubber 15.2% by weight was added to the first axial flow induced flow drum mixer.
Example 7
The difference from example 1 was that the method further comprises the steps of adding potassium hexadecyl phosphate in an amount of 0.05% by mass of the mixed system to the first axial flow guiding drum mixer and adding potassium hexadecyl phosphate in an amount of 0.01% by mass of the mixed system to the second axial flow guiding drum mixer, and the other operation conditions were the same.
Example 8
The difference from example 5 is that the method further comprises the step of adding tween-80 accounting for 0.03 percent of the mass of the mixing system into the first axial flow guide flow cylinder mixer and adding tween-80 accounting for 0.01 percent of the mass of the mixing system into the second axial flow guide flow cylinder mixer, and other operation conditions are the same.
The content of the halide salt (NaCl or NaBr) in the finished halogenated butyl rubber prepared in examples 1 to 8 was measured, and the measurement results are shown in table 1.
As shown in Table 1, after the halogenated butyl rubber is treated by the water washing process, the halogen salt content in the finished halogenated butyl rubber is 30-100 ppm. Example 1 compared to example 7 and example 5 compared to example 8 show that the halide salt content of the finished halogenated butyl rubber can be further reduced during the water wash by adding a surfactant to the mixing system.
The concentrations of bromide ions in the buffer tanks of high-concentration wastewater in examples 1 to 4 and 7 were measured, and the results are shown in table 2.
As seen from Table 2, the concentration of bromide ions in the high-concentration sewage buffer storage tank reaches 1.5-1.9 wt%, and compared with the bromide ion content of the external sewage in the conventional brominated butyl rubber production process of 0.5-0.9 wt%, the halogenated butyl rubber washing process provided by the embodiment of the invention can obviously improve the bromide ion content in the external waste water, and is beneficial to improving the recovery rate of subsequent bromine recovery and reducing the energy consumption of bromine recovery. Also, example 1 compared to example 7, shows that more bromide salt can be eluted during the water wash by adding a surfactant to the mixed system.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. A water washing process of halogenated butyl rubber is characterized by comprising the following steps:
adding alkali liquor and first washing water into halogenated glue solution containing hydrogen halide to obtain a first mixed system, wherein the pH value of the first mixed system is 8.0-10.0;
standing and separating the first mixed system to obtain a first water phase system and a first gel phase system, wherein the mass ratio of the first gel phase system to the first water phase system in the first mixed system is (2.0-7.0): 1; the first water phase system enters a wastewater treatment process;
adding second washing water into the first gel phase system to obtain a second mixed system;
standing and separating the second mixed system to obtain a second water phase system and a second gel phase system, wherein the mass ratio of the second gel phase system to the second water phase system in the second mixed system is (2.0-7.0): 1; the second water phase system enters a wastewater treatment process;
adding an auxiliary agent into the second gel phase system to obtain a third mixed system;
adding third washing water and hot steam into the third mixed system to carry out flash evaporation to remove the organic solvent;
then dewatering and drying to obtain the waste water and the finished product of halogenated butyl rubber;
the removal wastewater is recycled to be used as the first washing water, the second washing water and the third washing water;
the mixing process of the first mixing system is carried out in a first axial flow induced flow barrel mixer; the mixing process of the second mixing system is carried out in a second axial flow guide cylinder type mixer; the residence time of the materials in the first axial flow guide flow cylinder type mixer and the second axial flow guide flow cylinder type mixer is 0.5-5 min.
2. The process of claim 1, further comprising adding a surfactant to the first mixed system and the second mixed system, wherein the surfactant is an alkyl ester emulsifier or a polyol ester emulsifier.
3. The process of claim 1, further comprising the steps of: and heating and devolatilizing the first aqueous phase system and the second aqueous phase system by using the removed organic solvent so as to remove organic matters in the first aqueous phase system and the second aqueous phase system.
4. The process of claim 2, wherein the surfactant is added in an amount of 0.01 to 0.05% by weight of the first mixed system.
5. The process of claim 1, wherein the first rubber phase system contains 5.0-8.0 wt% water, and the second rubber phase system contains 5.0-8.0 wt% water.
6. The process of claim 5, wherein the halide ion content of the first aqueous system is 0.6 wt% to 2.0 wt%.
7. The water washing process of halogenated butyl rubber according to claim 6, wherein the content of halogen salt in the finished halogenated butyl rubber is 30-100 ppm.
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| CN102786618A (en) * | 2012-07-23 | 2012-11-21 | 华东理工大学 | Preparation method for brominated and chlorinated butyl rubber |
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| CN102786618A (en) * | 2012-07-23 | 2012-11-21 | 华东理工大学 | Preparation method for brominated and chlorinated butyl rubber |
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Application publication date: 20201117 Assignee: Panjin Xinhui New Material Co.,Ltd. Assignor: ZHEJIANG CENWAY NEW SYNTHETIC MATERIALS CO.,LTD. Contract record no.: X2023330000504 Denomination of invention: A Water Wash Process for Halogenated Butyl Rubber Granted publication date: 20220812 License type: Exclusive License Record date: 20230809 |