CN103739781B - A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber - Google Patents
A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber Download PDFInfo
- Publication number
- CN103739781B CN103739781B CN201310689686.5A CN201310689686A CN103739781B CN 103739781 B CN103739781 B CN 103739781B CN 201310689686 A CN201310689686 A CN 201310689686A CN 103739781 B CN103739781 B CN 103739781B
- Authority
- CN
- China
- Prior art keywords
- butadiene
- parts
- styrene
- preparation
- enters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the preparation method of a kind of rubber, particularly relate to the preparation method of a kind of non-contamination-type non-oil-charge styrene butadiene ribber.Sequentially include the following steps: blending butadiene and prepare → blend the preparation → polyreaction → unreacted monomer recovery → unreacted butadiene recovery → unreacted benzene ethylene recovery → environment-friendly type age resistor preparation → vulcanization accelerator preparation → mother liquor → cohesion → washing → dehydration → dry → briquetting → face inspection → packaging of styrene preparation → soap lye preparation → activator preparation → oxygen scavenger preparation → terminator preparation → oxidant and regulator.The preparation method of a kind of non-contamination-type non-oil-charge styrene butadiene ribber, optimizes serviceability, and product suitability is high.
Description
Technical field
The present invention relates to the preparation method of a kind of rubber, particularly relate to a kind of non-contamination-type non-oil-charge styrene-fourth two
The preparation method of alkene rubber.
Background technology
The production of SBR of emulsion polymerization starts from Germany, obtains and develops rapidly, is in the U.S., and the world is big for the second time
Before war terminates, Germany and the U.S. all use Buna-S technology full-boiled process emulsion polymerization technique to produce butadiene-styrene rubber, and Great War for the second time is tied
Shu Hou, the U.S., initially with cold process SBR of emulsion polymerization technique, uses redox initiation system as polymerization formula.Its
The SBR of emulsion polymerization of its country then develops later, be all just realize after the 1950's industrial.From
The full-boiled process polymerization of persulfate initiating system turns to the cold process of redox initiation system to be polymerized, and is to produce emulsion polymerized styrene butadiene rubber to gather
Close the breakthrough of technique.But some serviceability relative deficiency of product.
Summary of the invention
The present invention mainly solves the deficiencies in the prior art, it is provided that a kind of have good hot strength, wear-resisting
Performance and flexural property, be widely used in bright-colored and light rubber, such as tire sidewall, transparent rubber overshoes, adhesive plaster, doctor
Treat the preparation side of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber of goods and other colour or light-colour rubber
Method.
The above-mentioned technical problem of the present invention is mainly addressed by following technical proposals:
The preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber, sequentially includes the following steps:
(1), blend butadiene to prepare:
Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger control to deposit
Storing temperature is≤18 DEG C, blends butadiene with recovery butadiene preparation after alkali cleaning, and the purity controlling to blend butadiene is 91.0%
~97.0%, TBC content is≤10ppm, use to be polymerized;Reclaim purity >=78.0% of butadiene
During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.2~1.5 parts, mixed by pipeline, alkali liquor recycles;
(2), blend styrene to prepare:
Fresh benzene ethylene is stored in storage tank, by ammonia cold heat exchanger control storage temperature≤18 DEG C, fresh benzene ethylene with return
Receiving styrene preparation and blend styrene, controlling to blend styrene purity is 91.0%~97.0%, use to be polymerized;
Reclaim cinnamic purity >=87.0%, TBC≤10ppm;
(3), soap lye preparation:
Soap lye is prepared in groove bucket, and whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket
Add condensed water that 800 parts of temperature are 90 DEG C, 52 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, stir after mixing
Mixing, the time of stirring is 0.5 hour, adds the fatty acid of 70 parts, the KCL of 9.4 parts and the expansion of 2.56 parts after dissolving to Colophonium
Powder, is stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(4), activator preparation:
Activator is prepared in groove bucket, adds the desalted water of 992 parts, open stirring, add the EDTA of 1.4 parts in groove bucket
The rongalite of sodium ferrum and 6.3 parts is stirred sample analysis after 0.5 hour, qualified after send into surge tank and treat discharging;
(5), oxygen scavenger preparation:
Oxygen scavenger is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in oxygen scavenger configuration forward slot bucket
The desalted water of middle addition 87 parts, opens stirring, adds 2 parts of concentration and is the KOH solution of 48% and the oxygen scavenger of 11 parts is stirred 10
Sample analysis after minute, discharging treated by qualified rear surge tank of sending into;
(6), terminator preparation:
Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in terminator configuration forward slot bucket
The desalted water of middle addition 989 parts, opens stirring, adds terminator solution & stir sample analysis, conjunction after 10 minutes of 0.93 part
The NaNO of 0.2 part is added after lattice2, send into surge tank after stirring 10 minutes and treat discharging;
(7), oxidant and the preparation of regulator:
Oxidant and agent of adjusting are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding;
(8), polyreaction:
SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:
A, step (1) blend blending styrene 28.7 parts in butadiene 71.3 parts, step (2) online through static mixer
Mixing, regulator in soap lye 4.5 parts, step (7) in oxygen scavenger 0.06 part, step (3) in desalted water with 180 parts, step (5)
0.15 part, again after static mixer on-line mixing, is cooled to 8~12 DEG C through ammonia cooler, adds activator in step (4)
0.015 part, enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7);
B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, in each polymeric kettle, be furnished with the cold heat exchange of ammonia
Device control polymeric reaction temperature be 5~12 DEG C, by polymerization inventory and use polymeric kettle number control polymerization reaction time be 8~
11 hours, reaction pressure controlled 0.2~0.5MPa;
C, reach requirement conversion ratio 62~70% when polymerization, when Mooney point reaches 46~56, add afterwards in step (6) and terminate
Agent 0.065 part, completes polyreaction, formed solids content be 21.5~24.0% rubber cement deliver to unreacted monomer recovery unit;
(9), unreacted monomer reclaims:
Because polymerisation conversion is 62.0~70.0%, therefore product has 30.0~38.0% monomer do not participate in reaction,
These monomers are reclaimed;Monomer refers to butadiene and styrene;
(10), unreacted butadiene reclaims:
Rubber cement in step (9) enters pressure flash groove from still top, end, uses steam and desalted water to be configured to moist steam
Controlling flash temperature is 35~42 DEG C, carries out butadiene flash distillation when pressure is 0.10~0.16MPa, enters through the rubber cement of primary flash distillation
Entering the second pressure flash groove, control to carry out blood pressure lowering flash distillation when pressure is 0.015~0.025MPa, the butadiene flashed off enters
Compressor is compressed;
A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control pressure when being 0.015~0.025MPa
Carrying out vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.25~0.35MPa, send
Entering water cooler and be cooled to 30~38 DEG C, enter back into ammonia cooler and be cooled to 20~26 DEG C of condensations, butadiene fluid storage is at groove
Send in Tong in memory element i.e. step (1) and reclaim butadiene;
The butadiene that B, vacuum flashing groove flash off enters after butadiene vacuum pump is forced into 0.015~0.025MPa
Butadiene suction port of compressor carries out step A.
In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to inhale
Receiving the butadiene carried secretly in on-condensible gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve control
Pressure, discharge capacity 10~18m3/h;
(11), unreacted benzene ethylene recovery:
Latex after removing butadiene enters the first Styrene degassing tower top;
A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor by the low entrance of tower, latex and steam counter-flow warp
Column plate contacts, and abjection styrene vapor and water vapour are drawn from tower top;
B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, tower reactor goes out
Carry out latex and deliver to latex storage tank;
In C, step A, step B, tower top temperature controls at 55~65 DEG C, and pressure is 0.02~0.04MPa;Temperature in tower reactor
Degree is 60~70 DEG C, and pressure is 0.03~0.04MPa, and in tower, pressure is controlled by tower vacuum pump;
In D, step A, step B, styrene vapor and water vapour enter step through foam separator, the liquid trapped
Suddenly in the vacuum flashing groove in (10-A), the water cooled but device of gas phase be cooled to 38~45 DEG C enter back into ammonia cooler be cooled to 26~
32 DEG C, condense out liquid and enter styrene through styrene Suction cop and strain and wash rice device carries out styrene separate with water;
In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, will separate
The styrene got off is sent into styrene in step D and is strained wash rice device, in gas feeding step (10-B) in butadiene vacuum pump;
Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal through overflow launder,
Styrene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2);Styrene liquid stores up
Depositing groove bucket is maintained pressure 0.0002MPa to deposit by nitrogen;
(12), environment-friendly type age resistor preparation:
A, 48.6 parts of styrenated phenols are transported to heating chamber it are heated up to 65.0~70.0 DEG C, confirm that it has flowing
Property;
B, adding soap lye in 16.9 parts of steps (3) in groove bucket, beat slotted drum steam and heat, control flume barrel temperature is
60~65 DEG C, adding the styrenated phenol 48.6 parts in step A, be sufficiently stirred for 1 hour, mixing speed is 970r.p.m, adds
The desalted water entering 34.5 parts is stirred for 0.5 hour, analyze qualified after to send into surge tank to be used;
(13), vulcanization accelerator preparation:
Vulcanization accelerator is prepared in groove bucket, adds 100 parts of desalted waters to groove bucket and the sulfuration that 2 parts of concentration is 31% promotes
Agent stirring half an hour, mixing speed is 750r.p.m, after carry out sample analysis;
(14), mother liquor:
Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, in collection surface bucket, add 40 parts
Desalted water, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, uses steam
The temperature controlled in collection surface is 65 DEG C, adds the flocculation aid of 0.001 part, and adding concentrated sulphuric acid control ph is 3.3~3.7, follows
Ring 0.5 hour, forms mother solution;
(15), cohesion:
Environment-friendly type age resistor 0.45 in 70 parts of mother solution, step (12) in 37 parts of latex in step (11-B), step (14)
Vulcanization accelerator 0.013 part in part, flocculation aid 0.01 part, step (13), enters after pipeline mixes and reduces pipe and accelerate into
Collection surface, the temperature in collection surface is 60~68 DEG C, pH value is 3.2~3.7, stirs 15 minutes, and mixing speed is 101r.p.m,
Rear formation is loose, porous, spongy rubber granule form suspension with mother solution, and suspension is under stirring from upper end discharging opening
Entering conversion tank, the overflow of inverting groove top enters vibrosieve, makes micelle separate with major part mother solution, and Recycling Mother Solution re-uses;
(16), washing:
The micelle sent here from step (15) continuously enters sink, in sink add NaOH control ph be 4.3~
4.7, adding 40.0 parts of mother solution in step (14), after stirring 10 minutes, mixing speed is 101r.p.m, enters vibrosieve;
(17), dehydration:
Carrying out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, and controls
Chewing gum grain water content be less than or equal to 15%, micelle from dewaterer export out entrance wet-milling broken, rubber grain is crushed to 5~
After 50mm indefinite form sizing material, form wet sizing material, send into cyclone separator with feeding fan;
(18), it is dried:
A, wet sizing material in step (18) enter before drying baker on distributing device by gravity, by being arranged on drying baker feed end
Vibrating distributor be evenly distributed on drying baker carrier bar, by adjust drying baker carrier bar pace control sizing material fabric thickness
Being 80~150mm, wet micelle moves along with carrier bar, passes sequentially through 6 districts of drying baker by the order in a district to 6th district, and whirlwind divides
Suck above the waste gas self-desiccation case cooling zone that device is discharged, sequentially entered five through air heater by circulating fan, four,
Three, 2nd district, is evacuated to emission-control equipment by waste gas exhaust fan by humid air above first and secondth district;
It is 30~60 minutes that A, each district control drying time, and the baking temperature in drying baker one district is 75~90 DEG C, is dried
The baking temperature in case two district is 80~95 DEG C, the baking temperature in drying baker three district is 80~95 DEG C, the dry temperature in drying baker four district
Degree is 80~95 DEG C, the baking temperature in drying baker five district is 75~80 DEG C, 6th district adjust according to sizing material temperature, controls drying baker and goes out
Chewing gum material temperature degree is more than or equal to 45 DEG C with less than or equal to 60 DEG C;
C, sizing material, enter by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content less than 2.0%
Jigging conveyer is to packaging unit;
(19), briquetting:
A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, sizing material from point
The inclination sieve plate of glassware lower end, separates larger-size sizing material, and big sizing material is directly entered electronic scale weighing case and carries out thick feed,
The tiny sizing material spilt through sieve aperture is fallen on oscillating feeder, sends into electronic quantitative scale weight box by vibrating transportation, carries out essence
Feed;
B, when feed starts, top gate is opened, bottom hopper bottom door close, when weight reaches thick feed predetermined value
During 33.0Kg, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, the closedown of bottom hopper, rubber
Glue granule is put into cuber by transition hopper and is carried out briquetting process;After blowing terminates, bottom hopper cuts out, and top gate is beaten
Driving row new round weighing process, weight 35.0Kg of weighing into, precision is ± 0.175Kg, 180 pieces/h of speed of weighing;
C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form glue
Block;
(20), face inspection:
From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, warp
After manual detection, blob of viscose enters and rechecks scale, rejects the blob of viscose being unsatisfactory for component requirement, and blob of viscose enters metal detection from rechecking scale
Instrument carries out metal detection, and the blob of viscose that metal is contained in inside is rejected;
(21), packaging:
From the blob of viscose of metal detector discharging by track send into thin film packaging, blob of viscose use PE film encapsulating, prevent blob of viscose because of
Long-time placement causes surface adhesion paper bag, and after after thin film encapsulation, blob of viscose is sent into paper bag packing, coding by track, man power encasement goes out
Storehouse.
As preferably, in step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm;Purity >=
99.3%;Dimer≤1000ppm;TBC content 50~150ppm;In step (2), fresh benzene ethylene technical specification: purity >=
99.5%;TBC content 10~30ppm;In step (3), mixing speed is 105r.p.m;In step (5), it is passed through the speed of nitrogen
It is 2~4m3/h;In step (6), the speed being passed through nitrogen is 2~4m3/h。
Therefore, the preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber of the present invention, optimize and use
Performance, product suitability is high.
Detailed description of the invention
Below by embodiment, technical scheme is described in further detail.
Embodiment 1: the preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber, enters according to the following steps
OK:
(1), blend butadiene to prepare:
Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger control to deposit
Storing temperature is≤18 DEG C, blends butadiene with recovery butadiene preparation after alkali cleaning, and the purity controlling to blend butadiene is
91.0%, TBC content is≤10ppm, use to be polymerized;Reclaim purity >=78.0% of butadiene
During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.2 parts, mixed by pipeline, alkali liquor recycles;
(2), blend styrene to prepare:
Fresh benzene ethylene is stored in storage tank, by ammonia cold heat exchanger control storage temperature≤18 DEG C, fresh benzene ethylene with return
Receiving styrene preparation and blend styrene, controlling to blend styrene purity is 91.0%, use to be polymerized;
Reclaim cinnamic purity >=87.0%, TBC≤10ppm;
(3), soap lye preparation:
Soap lye is prepared in groove bucket, and whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket
Add condensed water that 800 parts of temperature are 90 DEG C, 52 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, stir after mixing
Mixing, the time of stirring is 0.5 hour, adds the fatty acid of 70 parts, the KCL of 9.4 parts and the expansion of 2.56 parts after dissolving to Colophonium
Powder, is stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(4), activator preparation:
Activator is prepared in groove bucket, adds the desalted water of 992 parts, open stirring, add the EDTA of 1.4 parts in groove bucket
The rongalite of sodium ferrum and 6.3 parts is stirred sample analysis after 0.5 hour, qualified after send into surge tank and treat discharging;
(5), oxygen scavenger preparation:
Oxygen scavenger is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in oxygen scavenger configuration forward slot bucket
The desalted water of middle addition 87 parts, opens stirring, adds 2 parts of concentration and is the KOH solution of 48% and the oxygen scavenger of 11 parts is stirred 10
Sample analysis after minute, discharging treated by qualified rear surge tank of sending into;
(6), terminator preparation:
Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in terminator configuration forward slot bucket
The desalted water of middle addition 989 parts, opens stirring, adds terminator solution & stir sample analysis, conjunction after 10 minutes of 0.93 part
The NaNO of 0.2 part is added after lattice2, send into surge tank after stirring 10 minutes and treat discharging;
(7), oxidant and the preparation of regulator:
Oxidant and agent of adjusting are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding;
(8), polyreaction:
SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:
A, step (1) blend blending styrene 28.7 parts in butadiene 71.3 parts, step (2) online through static mixer
Mixing, regulator in soap lye 4.5 parts, step (7) in oxygen scavenger 0.06 part, step (3) in desalted water with 180 parts, step (5)
0.15 part, again after static mixer on-line mixing, is cooled to 8~12 DEG C through ammonia cooler, adds activator in step (4)
0.015 part, enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7);
B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, in each polymeric kettle, be furnished with the cold heat exchange of ammonia
It is 5 DEG C that device controls polymeric reaction temperature, polymerization inventory and use polymeric kettle number controlling polymerization reaction time is 8 hours,
Reaction pressure controls at 0.2MPa;
C, when polymerization reaches requirement conversion ratio 62%, when Mooney point reaches 46, add terminator 0.065 in step (6) afterwards
Part, complete polyreaction, form the rubber cement that solids content is 21.5% and deliver to unreacted monomer recovery unit;
(9), unreacted monomer reclaims:
Because polymerisation conversion is 62.0%, therefore having 38.0% monomer not participate in reaction in product, these monomers give
Reclaim;Monomer refers to butadiene and styrene;
(10), unreacted butadiene reclaims:
Rubber cement in step (9) enters pressure flash groove from still top, end, uses steam and desalted water to be configured to moist steam
Controlling flash temperature is 35 DEG C, carries out butadiene flash distillation when pressure is 0.10MPa, enters the second pressure through the rubber cement of primary flash distillation
Flash tank, controls to carry out blood pressure lowering flash distillation when pressure is 0.015MPa, and the butadiene flashed off enters compressor and is compressed;
A, in pressure flash groove rubber cement out sends into vacuum flashing groove, controlling pressure is to reduce pressure during 0.015MPa
Flash distillation, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.25MPa, sends into water cooler cooling
To 30 DEG C, entering back into ammonia cooler and be cooled to 20 DEG C of condensations, butadiene fluid storage sends into memory element i.e. step in groove bucket
(1) butadiene is reclaimed in;
The butadiene that B, vacuum flashing groove flash off enters butadiene after butadiene vacuum pump is forced into 0.015MPa
Suction port of compressor carries out step A.
In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to inhale
Receiving the butadiene carried secretly in on-condensible gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve control
Pressure, discharge capacity 10m3/h;
(11), unreacted benzene ethylene recovery:
Latex after removing butadiene enters the first Styrene degassing tower top;
A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor by the low entrance of tower, latex and steam counter-flow warp
Column plate contacts, and abjection styrene vapor and water vapour are drawn from tower top;
B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, tower reactor goes out
Carry out latex and deliver to latex storage tank;
In C, step A, step B, tower top temperature controls at 55 DEG C, and pressure is 0.02MPa;Temperature in tower reactor is 60 DEG C, pressure
Power is 0.03MPa, and in tower, pressure is controlled by tower vacuum pump;
In D, step A, step B, styrene vapor and water vapour enter step through foam separator, the liquid trapped
Suddenly, in the vacuum flashing groove in (10-A), the water cooled but device of gas phase is cooled to 38 DEG C and enters back into ammonia cooler and be cooled to 26 DEG C, cold
Coagulate liquid to enter styrene through styrene Suction cop and strain and wash rice device carries out styrene separate with water;
In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, will separate
The styrene got off is sent into styrene in step D and is strained wash rice device, in gas feeding step (10-B) in butadiene vacuum pump;
Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal through overflow launder,
Styrene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2);Styrene liquid stores up
Depositing groove bucket is maintained pressure 0.0002MPa to deposit by nitrogen;
(12), environment-friendly type age resistor preparation:
A, 48.6 parts of styrenated phenols are transported to heating chamber it are heated up to 65.0 DEG C, confirm that it has mobility;
B, adding soap lye in 16.9 parts of steps (3) in groove bucket, beat slotted drum steam and heat, control flume barrel temperature is
60 DEG C, adding the styrenated phenol 48.6 parts in step A, be sufficiently stirred for 1 hour, mixing speed is 970r.p.m, adds
The desalted water of 34.5 parts is stirred for 0.5 hour, analyzes qualified rear feeding surge tank to be used;
(13), vulcanization accelerator preparation:
Vulcanization accelerator is prepared in groove bucket, adds 100 parts of desalted waters to groove bucket and the sulfuration that 2 parts of concentration is 31% promotes
Agent stirring half an hour, mixing speed is 750r.p.m, after carry out sample analysis;
(14), mother liquor:
Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, in collection surface bucket, add 40 parts
Desalted water, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, uses steam
The temperature controlled in collection surface is 65 DEG C, adds the flocculation aid of 0.001 part, and adding concentrated sulphuric acid control ph is 3.3, circulates 0.5
Hour, form mother solution;
(15), cohesion:
Environment-friendly type age resistor 0.45 in 70 parts of mother solution, step (12) in 37 parts of latex in step (11-B), step (14)
Vulcanization accelerator 0.013 part in part, flocculation aid 0.01 part, step (13), enters after pipeline mixes and reduces pipe and accelerate into
Collection surface, the temperature in collection surface is 60 DEG C, pH value is 3.2, stirs 15 minutes, and mixing speed is 101r.p.m, and rear formation is dredged
Pine, porous, spongy rubber granule form suspension with mother solution, and suspension enters from upper end discharging opening under stirring and converts
Groove, the overflow of inverting groove top enters vibrosieve, makes micelle separate with major part mother solution, and Recycling Mother Solution re-uses;
(16), washing:
The micelle sent here from step (15) continuously enters sink, adds NaOH control ph and be 4.3, add in sink
Entering 40.0 parts of mother solution in step (14), after stirring 10 minutes, mixing speed is 101r.p.m, enters vibrosieve;
(17), dehydration:
Carrying out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, and controls
Chewing gum grain water content is less than or equal to 15%, and it is broken that micelle exports out entrance wet-milling from dewaterer, rubber grain is crushed to 5mm not
After sizing sizing material, form wet sizing material, send into cyclone separator with feeding fan;
(18), it is dried:
A, wet sizing material in step (18) enter before drying baker on distributing device by gravity, by being arranged on drying baker feed end
Vibrating distributor be evenly distributed on drying baker carrier bar, by adjust drying baker carrier bar pace control sizing material fabric thickness
For 80mm, wet micelle moves along with carrier bar, passes sequentially through 6 districts of drying baker, cyclone separator by the order in a district to 6th district
Suck above the waste gas self-desiccation case cooling zone discharged, sequentially entered five through air heater by circulating fan, four, three,
2nd district, are evacuated to emission-control equipment by waste gas exhaust fan by humid air above first and secondth district;
A, each district control drying time be 30 minutes, the baking temperature in drying baker one district is 75 DEG C, drying baker two district
Baking temperature is 80 DEG C, the baking temperature in drying baker three district is 80 DEG C, the baking temperature in drying baker four district is 80 DEG C, drying baker five
The baking temperature in district is 75 DEG C, 6th district adjust according to sizing material temperature, control drying baker outlet sizing material temperature more than or equal to 45 DEG C and
Less than or equal to 60 DEG C;
C, sizing material, enter by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content less than 2.0%
Jigging conveyer is to packaging unit;
(19), briquetting:
A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, sizing material from point
The inclination sieve plate of glassware lower end, separates larger-size sizing material, and big sizing material is directly entered electronic scale weighing case and carries out thick feed,
The tiny sizing material spilt through sieve aperture is fallen on oscillating feeder, sends into electronic quantitative scale weight box by vibrating transportation, carries out essence
Feed;
B, when feed starts, top gate is opened, bottom hopper bottom door close, when weight reaches thick feed predetermined value
During 33.0Kg, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, the closedown of bottom hopper, rubber
Glue granule is put into cuber by transition hopper and is carried out briquetting process;After blowing terminates, bottom hopper cuts out, and top gate is beaten
Driving row new round weighing process, weight 35.0Kg of weighing into, precision is ± 0.175Kg, 180 pieces/h of speed of weighing;
C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form glue
Block;
(20), face inspection:
From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, warp
After manual detection, blob of viscose enters and rechecks scale, rejects the blob of viscose being unsatisfactory for component requirement, and blob of viscose enters metal detection from rechecking scale
Instrument carries out metal detection, and the blob of viscose that metal is contained in inside is rejected;
(21), packaging:
From the blob of viscose of metal detector discharging by track send into thin film packaging, blob of viscose use PE film encapsulating, prevent blob of viscose because of
Long-time placement causes surface adhesion paper bag, and after after thin film encapsulation, blob of viscose is sent into paper bag packing, coding by track, man power encasement goes out
Storehouse.
In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm;Purity >=99.3%;Dimer≤
1000ppm;TBC content 50ppm;In step (2), fresh benzene ethylene technical specification: purity >=99.5%;TBC content 10ppm;Step
Suddenly, in (3), mixing speed is 105r.p.m;In step (5), the speed being passed through nitrogen is 2~4m3/h;In step (6), it is passed through
The speed of nitrogen is 2~4m3/h。
Embodiment 2: the preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber, enters according to the following steps
OK:
(1), blend butadiene to prepare:
Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger control to deposit
Storing temperature is≤18 DEG C, blends butadiene with recovery butadiene preparation after alkali cleaning, and the purity controlling to blend butadiene is
95.0%, TBC content is≤10ppm, use to be polymerized;Reclaim purity >=78.0% of butadiene
During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.4 parts, mixed by pipeline, alkali liquor recycles;
(2), blend styrene to prepare:
Fresh benzene ethylene is stored in storage tank, by ammonia cold heat exchanger control storage temperature≤18 DEG C, fresh benzene ethylene with return
Receiving styrene preparation and blend styrene, controlling to blend styrene purity is 95.0%, use to be polymerized;
Reclaim cinnamic purity >=87.0%, TBC≤10ppm;
(3), soap lye preparation:
Soap lye is prepared in groove bucket, and whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket
Add condensed water that 800 parts of temperature are 90 DEG C, 52 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, stir after mixing
Mixing, the time of stirring is 0.5 hour, adds the fatty acid of 70 parts, the KCL of 9.4 parts and the expansion of 2.56 parts after dissolving to Colophonium
Powder, is stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(4), activator preparation:
Activator is prepared in groove bucket, adds the desalted water of 992 parts, open stirring, add the EDTA of 1.4 parts in groove bucket
The rongalite of sodium ferrum and 6.3 parts is stirred sample analysis after 0.5 hour, qualified after send into surge tank and treat discharging;
(5), oxygen scavenger preparation:
Oxygen scavenger is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in oxygen scavenger configuration forward slot bucket
The desalted water of middle addition 87 parts, opens stirring, adds 2 parts of concentration and is the KOH solution of 48% and the oxygen scavenger of 11 parts is stirred 10
Sample analysis after minute, discharging treated by qualified rear surge tank of sending into;
(6), terminator preparation:
Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in terminator configuration forward slot bucket
The desalted water of middle addition 989 parts, opens stirring, adds terminator solution & stir sample analysis, conjunction after 10 minutes of 0.93 part
The NaNO of 0.2 part is added after lattice2, send into surge tank after stirring 10 minutes and treat discharging;
(7), oxidant and the preparation of regulator:
Oxidant and agent of adjusting are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding;
(8), polyreaction:
SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:
A, step (1) blend blending styrene 28.7 parts in butadiene 71.3 parts, step (2) online through static mixer
Mixing, regulator in soap lye 4.5 parts, step (7) in oxygen scavenger 0.06 part, step (3) in desalted water with 180 parts, step (5)
0.15 part, again after static mixer on-line mixing, is cooled to 10 DEG C through ammonia cooler, adds activator in step (4)
0.015 part, enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7);
B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, in each polymeric kettle, be furnished with the cold heat exchange of ammonia
It is 10 DEG C that device controls polymeric reaction temperature, by polymerization inventory and to use polymeric kettle number to control polymerization reaction time be 10 little
Time, reaction pressure controls at 0.4MPa;
C, when polymerization reaches requirement conversion ratio 68%, when Mooney point reaches 50, add terminator 0.065 in step (6) afterwards
Part, complete polyreaction, form the rubber cement that solids content is 23.0% and deliver to unreacted monomer recovery unit;
(9), unreacted monomer reclaims:
Because polymerisation conversion is 68%, therefore having 32.0% monomer not participate in reaction in product, these monomers are returned
Receive;Monomer refers to butadiene and styrene;
(10), unreacted butadiene reclaims:
Rubber cement in step (9) enters pressure flash groove from still top, end, uses steam and desalted water to be configured to moist steam
Controlling flash temperature is 40 DEG C, carries out butadiene flash distillation when pressure is 0.13MPa, enters the second pressure through the rubber cement of primary flash distillation
Flash tank, controls to carry out blood pressure lowering flash distillation when pressure is 0.020MPa, and the butadiene flashed off enters compressor and is compressed;
A, in pressure flash groove rubber cement out sends into vacuum flashing groove, controlling pressure is to reduce pressure during 0.020MPa
Flash distillation, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.30MPa, sends into water cooler cooling
To 35 DEG C, entering back into ammonia cooler and be cooled to 24 DEG C of condensations, butadiene fluid storage sends into memory element i.e. step in groove bucket
(1) butadiene is reclaimed in;
The butadiene that B, vacuum flashing groove flash off enters butadiene after butadiene vacuum pump is forced into 0.020MPa
Suction port of compressor carries out step A.
In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to inhale
Receiving the butadiene carried secretly in on-condensible gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve control
Pressure, discharge capacity 15m3/h;
(11), unreacted benzene ethylene recovery:
Latex after removing butadiene enters the first Styrene degassing tower top;
A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor by the low entrance of tower, latex and steam counter-flow warp
Column plate contacts, and abjection styrene vapor and water vapour are drawn from tower top;
B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, tower reactor goes out
Carry out latex and deliver to latex storage tank;
In C, step A, step B, tower top temperature controls at 60 DEG C, and pressure is 0.03MPa;Temperature in tower reactor is 65 DEG C, pressure
Power is 0.035MPa, and in tower, pressure is controlled by tower vacuum pump;
In D, step A, step B, styrene vapor and water vapour enter step through foam separator, the liquid trapped
Suddenly, in the vacuum flashing groove in (10-A), the water cooled but device of gas phase is cooled to 40 DEG C and enters back into ammonia cooler and be cooled to 30 DEG C, cold
Coagulate liquid to enter styrene through styrene Suction cop and strain and wash rice device carries out styrene separate with water;
In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, will separate
The styrene got off is sent into styrene in step D and is strained wash rice device, in gas feeding step (10-B) in butadiene vacuum pump;
Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal through overflow launder,
Styrene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2);Styrene liquid stores up
Depositing groove bucket is maintained pressure 0.0002MPa to deposit by nitrogen;
(12), environment-friendly type age resistor preparation:
A, 48.6 parts of styrenated phenols are transported to heating chamber it are heated up to 68.0 DEG C, confirm that it has mobility;
B, adding soap lye in 16.9 parts of steps (3) in groove bucket, beat slotted drum steam and heat, control flume barrel temperature is
63 DEG C, adding the styrenated phenol 48.6 parts in step A, be sufficiently stirred for 1 hour, mixing speed is 970r.p.m, adds
The desalted water of 34.5 parts is stirred for 0.5 hour, analyzes qualified rear feeding surge tank to be used;
(13), vulcanization accelerator preparation:
Vulcanization accelerator is prepared in groove bucket, adds 100 parts of desalted waters to groove bucket and the sulfuration that 2 parts of concentration is 31% promotes
Agent stirring half an hour, mixing speed is 750r.p.m, after carry out sample analysis;
(14), mother liquor:
Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, in collection surface bucket, add 40 parts
Desalted water, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, uses steam
The temperature controlled in collection surface is 65 DEG C, adds the flocculation aid of 0.001 part, and adding concentrated sulphuric acid control ph is 3.5, circulates 0.5
Hour, form mother solution;
(15), cohesion:
Environment-friendly type age resistor 0.45 in 70 parts of mother solution, step (12) in 37 parts of latex in step (11-B), step (14)
Vulcanization accelerator 0.013 part in part, flocculation aid 0.01 part, step (13), enters after pipeline mixes and reduces pipe and accelerate into
Collection surface, the temperature in collection surface is 65 DEG C, pH value is 3.5, stirs 15 minutes, and mixing speed is 101r.p.m, and rear formation is dredged
Pine, porous, spongy rubber granule form suspension with mother solution, and suspension enters from upper end discharging opening under stirring and converts
Groove, the overflow of inverting groove top enters vibrosieve, makes micelle separate with major part mother solution, and Recycling Mother Solution re-uses;
(16), washing:
The micelle sent here from step (15) continuously enters sink, adds NaOH control ph and be 4.5, add in sink
Entering 40.0 parts of mother solution in step (14), after stirring 10 minutes, mixing speed is 101r.p.m, enters vibrosieve;
(17), dehydration:
Carrying out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, and controls
Chewing gum grain water content is less than or equal to 15%, and it is broken that micelle exports out entrance wet-milling from dewaterer, rubber grain is crushed to 20mm not
After sizing sizing material, form wet sizing material, send into cyclone separator with feeding fan;
(18), it is dried:
A, wet sizing material in step (18) enter before drying baker on distributing device by gravity, by being arranged on drying baker feed end
Vibrating distributor be evenly distributed on drying baker carrier bar, by adjust drying baker carrier bar pace control sizing material fabric thickness
For 100mm, wet micelle moves along with carrier bar, passes sequentially through 6 districts of drying baker, cyclone separator by the order in a district to 6th district
Suck above the waste gas self-desiccation case cooling zone discharged, sequentially entered five through air heater by circulating fan, four, three,
2nd district, are evacuated to emission-control equipment by waste gas exhaust fan by humid air above first and secondth district;
A, each district control drying time be 50 minutes, the baking temperature in drying baker one district is 80 DEG C, drying baker two district
Baking temperature is 90 DEG C, the baking temperature in drying baker three district is 90 DEG C, the baking temperature in drying baker four district is 90 DEG C, drying baker five
The baking temperature in district is 77 DEG C, 6th district adjust according to sizing material temperature, control drying baker outlet sizing material temperature more than or equal to 45 DEG C and
Less than or equal to 60 DEG C;
C, sizing material, enter by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content less than 2.0%
Jigging conveyer is to packaging unit;
(19), briquetting:
A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, sizing material from point
The inclination sieve plate of glassware lower end, separates larger-size sizing material, and big sizing material is directly entered electronic scale weighing case and carries out thick feed,
The tiny sizing material spilt through sieve aperture is fallen on oscillating feeder, sends into electronic quantitative scale weight box by vibrating transportation, carries out essence
Feed;
B, when feed starts, top gate is opened, bottom hopper bottom door close, when weight reaches thick feed predetermined value
During 33.0Kg, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, the closedown of bottom hopper, rubber
Glue granule is put into cuber by transition hopper and is carried out briquetting process;After blowing terminates, bottom hopper cuts out, and top gate is beaten
Driving row new round weighing process, weight 35.0Kg of weighing into, precision is ± 0.175Kg, 180 pieces/h of speed of weighing;
C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form glue
Block;
(20), face inspection:
From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, warp
After manual detection, blob of viscose enters and rechecks scale, rejects the blob of viscose being unsatisfactory for component requirement, and blob of viscose enters metal detection from rechecking scale
Instrument carries out metal detection, and the blob of viscose that metal is contained in inside is rejected;
(21), packaging:
From the blob of viscose of metal detector discharging by track send into thin film packaging, blob of viscose use PE film encapsulating, prevent blob of viscose because of
Long-time placement causes surface adhesion paper bag, and after after thin film encapsulation, blob of viscose is sent into paper bag packing, coding by track, man power encasement goes out
Storehouse.
In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm;Purity >=99.3%;Dimer≤
1000ppm;TBC content 100ppm;In step (2), fresh benzene ethylene technical specification: purity >=99.5%;TBC content 20ppm;
In step (3), mixing speed is 105r.p.m;In step (5), the speed being passed through nitrogen is 3m3/h;In step (6), it is passed through nitrogen
The speed of gas is 3m3/h。
Embodiment 3: the preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber, enters according to the following steps
OK:
(1), blend butadiene to prepare:
Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger control to deposit
Storing temperature is≤18 DEG C, blends butadiene with recovery butadiene preparation after alkali cleaning, and the purity controlling to blend butadiene is
97.0%, TBC content is≤10ppm, use to be polymerized;Reclaim purity >=78.0% of butadiene
During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.5 parts, mixed by pipeline, alkali liquor recycles;
(2), blend styrene to prepare:
Fresh benzene ethylene is stored in storage tank, by ammonia cold heat exchanger control storage temperature≤18 DEG C, fresh benzene ethylene with return
Receiving styrene preparation and blend styrene, controlling to blend styrene purity is 97.0%, use to be polymerized;
Reclaim cinnamic purity >=87.0%, TBC≤10ppm;
(3), soap lye preparation:
Soap lye is prepared in groove bucket, and whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, in groove bucket
Add condensed water that 800 parts of temperature are 90 DEG C, 52 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, stir after mixing
Mixing, the time of stirring is 0.5 hour, adds the fatty acid of 70 parts, the KCL of 9.4 parts and the expansion of 2.56 parts after dissolving to Colophonium
Powder, is stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(4), activator preparation:
Activator is prepared in groove bucket, adds the desalted water of 992 parts, open stirring, add the EDTA of 1.4 parts in groove bucket
The rongalite of sodium ferrum and 6.3 parts is stirred sample analysis after 0.5 hour, qualified after send into surge tank and treat discharging;
(5), oxygen scavenger preparation:
Oxygen scavenger is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in oxygen scavenger configuration forward slot bucket
The desalted water of middle addition 87 parts, opens stirring, adds 2 parts of concentration and is the KOH solution of 48% and the oxygen scavenger of 11 parts is stirred 10
Sample analysis after minute, discharging treated by qualified rear surge tank of sending into;
(6), terminator preparation:
Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, to groove bucket in terminator configuration forward slot bucket
The desalted water of middle addition 989 parts, opens stirring, adds terminator solution & stir sample analysis, conjunction after 10 minutes of 0.93 part
The NaNO of 0.2 part is added after lattice2, send into surge tank after stirring 10 minutes and treat discharging;
(7), oxidant and the preparation of regulator:
Oxidant and agent of adjusting are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding;
(8), polyreaction:
SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:
A, step (1) blend blending styrene 28.7 parts in butadiene 71.3 parts, step (2) online through static mixer
Mixing, regulator in soap lye 4.5 parts, step (7) in oxygen scavenger 0.06 part, step (3) in desalted water with 180 parts, step (5)
0.15 part, again after static mixer on-line mixing, is cooled to 10 DEG C through ammonia cooler, adds activator in step (4)
0.015 part, enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7);
B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, in each polymeric kettle, be furnished with the cold heat exchange of ammonia
It is 10 DEG C that device controls polymeric reaction temperature, by polymerization inventory and to use polymeric kettle number to control polymerization reaction time be 10 little
Time, reaction pressure controls at 0.4MPa;
C, when polymerization reaches requirement conversion ratio 70%, when Mooney point reaches 56, add terminator 0.065 in step (6) afterwards
Part, complete polyreaction, formed solids content be 21.5~24.0% rubber cement deliver to unreacted monomer recovery unit;
(9), unreacted monomer reclaims:
Because polymerisation conversion is 70.0%, therefore having 30.0% monomer not participate in reaction in product, these monomers give
Reclaim;Monomer refers to butadiene and styrene;
(10), unreacted butadiene reclaims:
Rubber cement in step (9) enters pressure flash groove from still top, end, uses steam and desalted water to be configured to moist steam
Controlling flash temperature is 42 DEG C, carries out butadiene flash distillation when pressure is 0.16MPa, enters the second pressure through the rubber cement of primary flash distillation
Flash tank, controls to carry out blood pressure lowering flash distillation when pressure is 0.025MPa, and the butadiene flashed off enters compressor and is compressed;
A, in pressure flash groove rubber cement out sends into vacuum flashing groove, controlling pressure is to reduce pressure during 0.025MPa
Flash distillation, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.35MPa, sends into water cooler cooling
To 38 DEG C, entering back into ammonia cooler and be cooled to 26 DEG C of condensations, butadiene fluid storage sends into memory element i.e. step in groove bucket
(1) butadiene is reclaimed in;
The butadiene that B, vacuum flashing groove flash off enters butadiene after butadiene vacuum pump is forced into 0.025MPa
Suction port of compressor carries out step A.
In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to inhale
Receiving the butadiene carried secretly in on-condensible gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve control
Pressure, discharge capacity 18m3/h;
(11), unreacted benzene ethylene recovery:
Latex after removing butadiene enters the first Styrene degassing tower top;
A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor by the low entrance of tower, latex and steam counter-flow warp
Column plate contacts, and abjection styrene vapor and water vapour are drawn from tower top;
B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, tower reactor goes out
Carry out latex and deliver to latex storage tank;
In C, step A, step B, tower top temperature controls at 65 DEG C, and pressure is 0.04MPa;Temperature in tower reactor is 70 DEG C, pressure
Power is 0.04MPa, and in tower, pressure is controlled by tower vacuum pump;
In D, step A, step B, styrene vapor and water vapour enter step through foam separator, the liquid trapped
Suddenly, in the vacuum flashing groove in (10-A), the water cooled but device of gas phase is cooled to 38~45 DEG C and enters back into ammonia cooler and be cooled to 32
DEG C, condense out liquid and enter styrene through styrene Suction cop and strain and wash rice device carries out styrene separate with water;
In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, will separate
The styrene got off is sent into styrene in step D and is strained wash rice device, in gas feeding step (10-B) in butadiene vacuum pump;
Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal through overflow launder,
Styrene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2);Styrene liquid stores up
Depositing groove bucket is maintained pressure 0.0002MPa to deposit by nitrogen;
(12), environment-friendly type age resistor preparation:
A, 48.6 parts of styrenated phenols are transported to heating chamber it are heated up to 70.0 DEG C, confirm that it has mobility;
B, adding soap lye in 16.9 parts of steps (3) in groove bucket, beat slotted drum steam and heat, control flume barrel temperature is
65 DEG C, adding the styrenated phenol 48.6 parts in step A, be sufficiently stirred for 1 hour, mixing speed is 970r.p.m, adds
The desalted water of 34.5 parts is stirred for 0.5 hour, analyzes qualified rear feeding surge tank to be used;
(13), vulcanization accelerator preparation:
Vulcanization accelerator is prepared in groove bucket, adds 100 parts of desalted waters to groove bucket and the sulfuration that 2 parts of concentration is 31% promotes
Agent stirring half an hour, mixing speed is 750r.p.m, after carry out sample analysis;
(14), mother liquor:
Confirm that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, in collection surface bucket, add 40 parts
Desalted water, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, uses steam
The temperature controlled in collection surface is 65 DEG C, adds the flocculation aid of 0.001 part, and adding concentrated sulphuric acid control ph is 3.7, circulates 0.5
Hour, form mother solution;
(15), cohesion:
Environment-friendly type age resistor 0.45 in 70 parts of mother solution, step (12) in 37 parts of latex in step (11-B), step (14)
Vulcanization accelerator 0.013 part in part, flocculation aid 0.01 part, step (13), enters after pipeline mixes and reduces pipe and accelerate into
Collection surface, the temperature in collection surface is 68 DEG C, pH value is 3.7, stirs 15 minutes, and mixing speed is 101r.p.m, and rear formation is dredged
Pine, porous, spongy rubber granule form suspension with mother solution, and suspension enters from upper end discharging opening under stirring and converts
Groove, the overflow of inverting groove top enters vibrosieve, makes micelle separate with major part mother solution, and Recycling Mother Solution re-uses;
(16), washing:
The micelle sent here from step (15) continuously enters sink, adds NaOH control ph and be 4.7, add in sink
Entering 40.0 parts of mother solution in step (14), after stirring 10 minutes, mixing speed is 101r.p.m, enters vibrosieve;
(17), dehydration:
Carrying out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, and controls
Chewing gum grain water content is less than or equal to 15%, and it is broken that micelle exports out entrance wet-milling from dewaterer, rubber grain is crushed to 50mm not
After sizing sizing material, form wet sizing material, send into cyclone separator with feeding fan;
(18), it is dried:
A, wet sizing material in step (18) enter before drying baker on distributing device by gravity, by being arranged on drying baker feed end
Vibrating distributor be evenly distributed on drying baker carrier bar, by adjust drying baker carrier bar pace control sizing material fabric thickness
For 150mm, wet micelle moves along with carrier bar, passes sequentially through 6 districts of drying baker, cyclone separator by the order in a district to 6th district
Suck above the waste gas self-desiccation case cooling zone discharged, sequentially entered five through air heater by circulating fan, four, three,
2nd district, are evacuated to emission-control equipment by waste gas exhaust fan by humid air above first and secondth district;
A, each district control drying time be 60 minutes, the baking temperature in drying baker one district is 90 DEG C, drying baker two district
Baking temperature is 95 DEG C, the baking temperature in drying baker three district is 95 DEG C, the baking temperature in drying baker four district is 95 DEG C, drying baker five
The baking temperature in district is 80 DEG C, 6th district adjust according to sizing material temperature, control drying baker outlet sizing material temperature more than or equal to 45 DEG C and
Less than or equal to 60 DEG C;
C, sizing material, enter by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content less than 2.0%
Jigging conveyer is to packaging unit;
(19), briquetting:
A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, sizing material from point
The inclination sieve plate of glassware lower end, separates larger-size sizing material, and big sizing material is directly entered electronic scale weighing case and carries out thick feed,
The tiny sizing material spilt through sieve aperture is fallen on oscillating feeder, sends into electronic quantitative scale weight box by vibrating transportation, carries out essence
Feed;
B, when feed starts, top gate is opened, bottom hopper bottom door close, when weight reaches thick feed predetermined value
During 33.0Kg, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, the closedown of bottom hopper, rubber
Glue granule is put into cuber by transition hopper and is carried out briquetting process;After blowing terminates, bottom hopper cuts out, and top gate is beaten
Driving row new round weighing process, weight 35.0Kg of weighing into, precision is ± 0.175Kg, 180 pieces/h of speed of weighing;
C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form glue
Block;
(20), face inspection:
From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, warp
After manual detection, blob of viscose enters and rechecks scale, rejects the blob of viscose being unsatisfactory for component requirement, and blob of viscose enters metal detection from rechecking scale
Instrument carries out metal detection, and the blob of viscose that metal is contained in inside is rejected;
(21), packaging:
From the blob of viscose of metal detector discharging by track send into thin film packaging, blob of viscose use PE film encapsulating, prevent blob of viscose because of
Long-time placement causes surface adhesion paper bag, and after after thin film encapsulation, blob of viscose is sent into paper bag packing, coding by track, man power encasement goes out
Storehouse.
In step (1), fresh butadiene technical specification: gas phase oxygen content≤2000ppm;Purity >=99.3%;Dimer≤
1000ppm;TBC content 150ppm;In step (2), fresh benzene ethylene technical specification: purity >=99.5%;TBC content 30ppm;
In step (3), mixing speed is 105r.p.m;In step (5), the speed being passed through nitrogen is 4m3/h;In step (6), it is passed through nitrogen
The speed of gas is 4m3/h。
Claims (2)
1. the preparation method of a non-contamination-type non-oil-charge type styrene-butadiene rubber, it is characterised in that enter according to the following steps
OK:
(1), blend butadiene to prepare:
Being stored in spherical tank by fresh butadiene, the storage pressure of spherical tank is≤0.36MPa, ammonia cold heat exchanger control storage temperature
Degree for≤18 DEG C, after alkali cleaning with reclaim butadiene preparation and blend butadiene, control to blend the purity of butadiene be 91.0%~
97.0%, TBC content is≤10ppm, use to be polymerized;Reclaim purity >=78.0% of butadiene
During alkali cleaning: butadiene: 10%NaOH solution=1 part: 1.2~1.5 parts, mixed by pipeline, alkali liquor recycles;
Fresh butadiene technical specification: gas phase oxygen content≤2000ppm;Purity >=99.3%;Dimer≤1000ppm;TBC contains
Amount 50~150ppm;
(2), blend styrene to prepare:
Fresh benzene ethylene is stored in storage tank, ammonia cold heat exchanger control storage temperature≤18 DEG C, fresh benzene ethylene and recovery benzene
Ethylene preparation blends styrene, and controlling to blend styrene purity is 91.0%~97.0%, use to be polymerized;
Reclaim cinnamic purity >=87.0%, TBC≤10ppm;
Fresh benzene ethylene technical specification: purity >=99.5%;TBC content 10~30ppm;
(3), soap lye preparation:
Soap lye is prepared in groove bucket, and whole process for preparation is 83 DEG C by steam computer heating control groove temperature within the barrel, adds in groove bucket
800 parts of temperature be the condensed water of 90 DEG C, 52 parts of concentration be 48.0% KOH solution and the Colophonium of 50 parts, be stirred after mixing,
The time of stirring is 0.5 hour, adds the fatty acid of 70 parts, the KCl of 9.4 parts and the diffusion of 2.56 parts after dissolving to Colophonium
Agent, is stirred for sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(4), activator preparation:
Activator is prepared in groove bucket, adds the desalted water of 992 parts, open stirring, add the EDETATE SODIUM ferrum of 1.4 parts in groove bucket
Rongalite with 6.3 parts is stirred sample analysis after 0.5 hour, and discharging treated by qualified rear surge tank of sending into;
(5), oxygen scavenger preparation:
Oxygen scavenger is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, add in groove bucket in oxygen scavenger configuration forward slot bucket
Enter the desalted water of 87 parts, open stirring, add 2 parts of concentration and be the KOH solution of 48% and the oxygen scavenger of 11 parts is stirred 10 minutes
Rear sample analysis, discharging treated by qualified rear surge tank of sending into;
(6), terminator preparation:
Terminator is prepared in groove bucket, is passed through nitrogen and has stoped oxygen to enter, add in groove bucket in terminator configuration forward slot bucket
Enter the desalted water of 989 parts, open stirring, add the terminator solution & stir of 0.93 part sample analysis after 10 minutes, qualified after
Add the NaNO of 0.2 part2, send into surge tank after stirring 10 minutes and treat discharging;
(7), oxidant and the preparation of regulator:
Oxidant and regulator are stored in groove bucket, use nitrogen to maintain the pressure of 0.85MPa, by nitrogen pressure feeding;
(8), polyreaction:
SBR styrene butadiene rubbers polymerization employing emulsion polymerization at low temperature:
A, step (1) blend blending styrene 28.7 parts in butadiene 71.3 parts, step (2) mix online through static mixer
Close, regulator in soap lye 4.5 parts, step (7) in oxygen scavenger 0.06 part, step (3) in desalted water with 180 parts, step (5)
0.15 part, again after static mixer on-line mixing, is cooled to 8~12 DEG C through ammonia cooler, adds activator in step (4)
0.015 part, enter the first reactor, be simultaneously introduced 0.05 part of initiation reaction of oxidant in step (7);
B, step A enter in polymeric kettle after initiation reaction and completes polyreaction, in each polymeric kettle, be furnished with ammonia cold heat exchanger control
Polymeric reaction temperature processed is 5~12 DEG C, by polymerization inventory and to use polymeric kettle number to control polymerization reaction time be 8~11 little
Time, reaction pressure controls 0.2~0.5MPa;
C, when polymerization reaches requirement conversion ratio 62~70%, when Mooney point reaches 46~56, add terminator in step (6) afterwards
0.065 part, complete polyreaction, formed solids content be 21.5~24.0% rubber cement deliver to unreacted monomer recovery unit;
(9), unreacted monomer reclaims:
Because polymerisation conversion is 62.0~70.0%, therefore product has 30.0~38.0% monomer do not participate in reaction, these
Monomer is reclaimed;Monomer refers to butadiene and styrene;
(10), unreacted butadiene reclaims:
Rubber cement in step (9) enters pressure flash groove from still top, end, uses steam and desalted water to be configured to moist steam control
Flash temperature is 35~42 DEG C, carries out butadiene flash distillation when pressure is 0.10~0.16MPa, enters the through the rubber cement of primary flash distillation
Two pressure flash grooves, control to carry out blood pressure lowering flash distillation when pressure is 0.015~0.025MPa, and the butadiene flashed off enters compression
Machine is compressed;
A, in pressure flash groove rubber cement out sends into vacuum flashing groove, control to carry out when pressure is 0.015~0.025MPa
Vacuum flashing, the butadiene that pressure flash groove flashes off enters butadiene compressor and is forced into 0.25~0.35MPa, sends into water
Cooler is cooled to 30~38 DEG C, enters back into ammonia cooler and is cooled to 20~26 DEG C of condensations, and butadiene fluid storage is in groove bucket
Send into and memory element i.e. step (1) reclaims butadiene;
The butadiene that B, vacuum flashing groove flash off enters fourth two after butadiene vacuum pump is forced into 0.015~0.025MPa
Alkene suction port of compressor carries out step A;
In C, step A butadiene groove bucket, butadiene enters tail gas absorber with the most recyclable noble gas, uses kerosene to absorb not
The butadiene carried secretly in solidifying gas, kerosene recycles in system, and unabsorbed on-condensible gas is adjusted valve and controls pressure,
Discharge capacity 10~18m3/h;
(11), unreacted benzene ethylene recovery:
Latex after removing butadiene enters the first Styrene degassing tower top;
A, degassing desalted water and low-pressure steam are configured to moistening saturated vapor and are entered by the bottom of tower, and latex and steam counter-flow are through column plate
Contact, abjection styrene vapor and water vapour are drawn from tower top;
B, entered by the first Styrene degassing tower tower reactor out latex second Styrene degassing tower repeat step A, tower reactor out glue
Breast delivers to latex storage tank;
In C, step A, step B, tower top temperature controls at 55~65 DEG C, and pressure is 0.02~0.04MPa;Temperature in tower reactor is
60~70 DEG C, pressure is 0.03~0.04MPa, and in tower, pressure is controlled by tower vacuum pump;
In D, step A, step B, styrene vapor and water vapour enter step through foam separator, the liquid trapped
(10-A), in the vacuum flashing groove in, the water cooled but device of gas phase is cooled to 38~45 DEG C and enters back into ammonia cooler and be cooled to 26~32
DEG C, condense out liquid and enter styrene through styrene Suction cop and strain and wash rice device carries out styrene separate with water;
In E, step D, gas enters tower vacuum pump after tower vacuum pump supercharging and seals water pot, after gas-liquid separation, will separate
Styrene send into styrene in step D and strain wash rice device, gas is sent in step (10-B) in butadiene vacuum pump;
Condensed fluid during styrene strains wash rice device in F, step D is after being continuously separated, and sewage delivers to sewage disposal, benzene second through overflow launder
Alkene enters to send in styrene liquid storing tank bucket and reclaims styrene in memory element i.e. step (2);Styrene liquid storing tank
Bucket is maintained pressure 0.0002MPa to deposit by nitrogen;
(12), environment-friendly type age resistor preparation:
A, 48.6 parts of styrenated phenols are transported to heating chamber it are heated up to 65.0~70.0 DEG C, confirm that it has mobility;
B, in groove bucket, add soap lye in 16.9 parts of steps (3), beat slotted drum steam and heat, control flume barrel temperature be 60~
65 DEG C, adding the styrenated phenol 48.6 parts in step A, be sufficiently stirred for 1 hour, mixing speed is 970r.p.m, adds
The desalted water of 34.5 parts is stirred for 0.5 hour, analyzes qualified rear feeding surge tank to be used;
(13), vulcanization accelerator preparation:
Vulcanization accelerator is prepared in groove bucket, adds 100 parts of desalted waters to groove bucket and the vulcanization accelerator that 2 parts of concentration is 31% stirs
Mixing half an hour, mixing speed is 750r.p.m, after carry out sample analysis;
(14), mother liquor:
Confirming that collection surface, conversion tank, mother liquor tank bottom drain valve, normally close valve are turned off, in collection surface bucket, addition 40 parts is de-
Saline, desalted water sequentially enters collection surface, conversion tank, opens stirring, ON cycle, 60 parts/h of circulating load, uses automatic steam control
Temperature in collection surface is 65 DEG C, adds the flocculation aid of 0.001 part, and adding concentrated sulphuric acid control ph is 3.3~3.7, circulates 0.5
Hour, form mother solution;
(15), cohesion:
0.45 part of environment-friendly type age resistor in 70 parts of mother solution, step (12) in 37 parts of latex in step (11-B), step (14), help
Vulcanization accelerator 0.013 part in solidifying agent 0.01 part, step (13), enters after pipeline mixes and reduces pipe and accelerate into cohesion
Groove, the temperature in collection surface is 60~68 DEG C, pH value is 3.2~3.7, stirs 15 minutes, and mixing speed is 101r.p.m, after
Forming loose, porous, spongy rubber granule and mother solution formation suspension, suspension enters from upper end discharging opening under stirring
Entering conversion tank, the overflow of inverting groove top enters vibrosieve, makes micelle separate with major part mother solution, and Recycling Mother Solution re-uses;
(16), washing:
The micelle sent here from step (15) continuously enters sink, add in sink NaOH control ph be 4.3~4.7,
Adding 40.0 parts of mother solution in step (14), after stirring 10 minutes, mixing speed is 101r.p.m, enters vibrosieve;
(17), dehydration:
Carrying out micelle entrance dewaterer from step (16) to be dehydrated, dewaterer selects screw extruding mode to be dehydrated, and controls chewing gum
Grain water content is less than or equal to 15%, and it is broken that micelle exports out entrance wet-milling from dewaterer, rubber grain is crushed to 5~50mm not
After sizing sizing material, form wet sizing material, send into cyclone separator with feeding fan;
(18), it is dried:
A, wet sizing material in step (18) enter before drying baker on distributing device by gravity, by being arranged on shaking of drying baker feed end
Driven distributing device is evenly distributed on drying baker carrier bar, is 80 by adjust drying baker carrier bar pace controlling sizing material fabric thickness
~150mm, wet micelle moves along with carrier bar, passes sequentially through 6 districts of drying baker, cyclone separator by the order in a district to 6th district
Suck above the waste gas self-desiccation case cooling zone discharged, sequentially entered five through air heater by circulating fan, four, three,
2nd district, are evacuated to emission-control equipment by waste gas exhaust fan by humid air above first and secondth district;
A, each district control drying time be 30~60 minutes, the baking temperature in drying baker one district is 75~90 DEG C, drying baker two
The baking temperature in district is 80~95 DEG C, the baking temperature in drying baker three district is 80~95 DEG C, the baking temperature in drying baker four district is
80~95 DEG C, the baking temperature in drying baker five district be 75~80 DEG C, 6th district adjust according to sizing material temperature, control drying baker and go out chewing gum
Material temperature degree is more than or equal to 45 DEG C with less than or equal to 60 DEG C;
C, sizing material less than 2.0%, are entered vibration by playing after disintegrating machine extremely conjunction material conveyer played by glue machine to drying baker afterbody water content
Conveyer is to packaging unit;
(19), briquetting:
A, the sizing material sent here from step (18) fall to jigging conveyer and sizing material are delivered to powder device of weighing, and sizing material is from tripper
The inclination sieve plate of lower end, separates larger-size sizing material, and big sizing material is directly entered electronic scale weighing case and carries out thick feed, through sieve
The tiny sizing material that hole spills is fallen on oscillating feeder, sends into electronic quantitative scale weight box by vibrating transportation, carries out essence feed;
B, when feed starts, top gate is opened, bottom hopper bottom door close, when weight reaches thick feed predetermined value 33.0Kg
Time, feeding machine carries out thin feed, when weight reaches predetermined value 35.0Kg, and top closing gate, the closedown of bottom hopper, rubber grain
Put into cuber by transition hopper and carry out briquetting process;After blowing terminates, bottom hopper cuts out, and top gate is opened and carried out
New round weighing process, weight 35.0Kg of weighing, precision is ± 0.175Kg, 180 pieces/h of speed of weighing;
C, charging enter cuber after weighing and carry out briquetting, press chamber a size of 700 × 350 × 190mm, form blob of viscose;
(20), face inspection:
From step (19) blob of viscose injection out, it is delivered to manual detection, surface abnormalities blob of viscose rejecting is processed, through artificial
After detection, blob of viscose enters and rechecks scale, rejects the blob of viscose being unsatisfactory for component requirement, and blob of viscose enters metal detector from reinspection scale and enters
Row metal detects, and the internal blob of viscose containing metal is rejected;
(21), packaging:
Being sent into thin film packaging from the blob of viscose of metal detector discharging by track, blob of viscose uses the encapsulating of PE film, prevents blob of viscose because of time long
Between place and cause surface adhesion paper bag, after thin film encapsulation, blob of viscose is sent into man power encasement's outbound after paper bag packing, coding by track.
The preparation method of a kind of non-contamination-type non-oil-charge type styrene-butadiene rubber the most according to claim 1, it is special
Levying and be: in step (3), mixing speed is 105r.p.m;In step (5), the speed being passed through nitrogen is 2~4m3/h;Step
(6), in, the speed being passed through nitrogen is 2~4m3/h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310689686.5A CN103739781B (en) | 2013-12-17 | 2013-12-17 | A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310689686.5A CN103739781B (en) | 2013-12-17 | 2013-12-17 | A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103739781A CN103739781A (en) | 2014-04-23 |
CN103739781B true CN103739781B (en) | 2016-09-21 |
Family
ID=50496859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310689686.5A Expired - Fee Related CN103739781B (en) | 2013-12-17 | 2013-12-17 | A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103739781B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111548449A (en) * | 2020-05-22 | 2020-08-18 | 浙江维泰橡胶有限公司 | Method for preparing deep-color high-strength styrene-butadiene rubber |
CN114230740B (en) * | 2021-12-27 | 2023-09-08 | 广东众和高新科技股份公司 | Transparent impact-resistant styrene-butadiene resin and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1425701A (en) * | 2001-12-14 | 2003-06-25 | 中国石化集团齐鲁石油化工公司 | Process for preparing lacto styrene butadiene rubber of different bound styrene content |
-
2013
- 2013-12-17 CN CN201310689686.5A patent/CN103739781B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1425701A (en) * | 2001-12-14 | 2003-06-25 | 中国石化集团齐鲁石油化工公司 | Process for preparing lacto styrene butadiene rubber of different bound styrene content |
Also Published As
Publication number | Publication date |
---|---|
CN103739781A (en) | 2014-04-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103303942B (en) | Method and device for recycling ammonium chloride from glycine mother liquor | |
CN103739781B (en) | A kind of preparation method of non-contamination-type non-oil-charge type styrene-butadiene rubber | |
CN105622825B (en) | Produce device and its production technology and the application of polyvinyl chloride interpolymer paste resin | |
CN103755871B (en) | A kind of preparation method of high stability SBR styrene butadiene rubbers | |
CN106512457A (en) | Four-effect concentration-crystallization-coupled system for threonine and operation process thereof | |
CN109609188A (en) | Wet process acetylene calcium carbide residues processing technique | |
CN103739782B (en) | A kind of environmental-friendtype type styrene-butadiene rubber preparation method | |
CN104610996A (en) | Novel process for refining oil through continuous catalytic cracking and recovery utilization of waste plastics | |
CN105771304A (en) | Double-effect countercurrent evaporation crystallization system for monosodium glutamate and working process thereof | |
CN112175125A (en) | Preparation process of polypropylene material | |
CN105693899B (en) | The device and its production method of micro- outstanding newborn method production PVC paste resin | |
CN103724542B (en) | A kind of preparation method of dark SBR styrene butadiene rubbers | |
CN112898551B (en) | Post-production treatment device and method for semi-aromatic polyester-polycarbonate copolymer | |
CN102303382B (en) | Method for recycling garbage plastics and special equipment | |
CN104151487A (en) | Water-phase suspension production system and method for acrylonitrile polymer for PNA carbon fiber precursor | |
CN110548331A (en) | method and device for separating polymer in slurry method polyethylene production process | |
CN205420252U (en) | A apparatus for producing for polyvinyl chloride seed law paste resin | |
CN209411799U (en) | A kind of preparation system of feed addictive calcium sulfate | |
CN104528770A (en) | Mirabilite dehydration method based on gas-liquid direct heat exchange | |
CN212334610U (en) | Steam gyration sodium sulfate drying system | |
CN102153707A (en) | Method for preparing large-particle-size high-impact-resistance MBS resin | |
CN110498626A (en) | A kind of production method of alpha semi-hydrated gypsum | |
CN106432839A (en) | Novel production method of environment-friendly oil-extended styrene-butadiene rubber | |
CN103570940B (en) | The processing method of the Polymerization Waste that a kind of p-aramid fiber produces in polymerization production process | |
CN105819448B (en) | A kind of method that high-purity carborundum is extracted from crystalline silicon cutting waste mortar |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160921 Termination date: 20171217 |
|
CF01 | Termination of patent right due to non-payment of annual fee |