CN105693899B - The device and its production method of micro- outstanding newborn method production PVC paste resin - Google Patents
The device and its production method of micro- outstanding newborn method production PVC paste resin Download PDFInfo
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- CN105693899B CN105693899B CN201610208623.7A CN201610208623A CN105693899B CN 105693899 B CN105693899 B CN 105693899B CN 201610208623 A CN201610208623 A CN 201610208623A CN 105693899 B CN105693899 B CN 105693899B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/24—Treatment of polymer suspensions
Abstract
The present invention relates to when a kind of device and production method for producing polyvinyl chloride, the device and production method of particularly micro- outstanding newborn method production PVC paste resin.Polymeric kettle is connected with blowpit, gas holder, waste water collection tank respectively, waste water collection tank is connected with stripper, stripper is connected with polymeric kettle, blowpit is connected with removing tower, waste water collection tank and defoaming mechanism respectively, removing tower is connected with latex groove and gas holder respectively, latex groove is connected with drying tower, and drying tower is connected with waste water collection tank.Production method, it is controlled by DCS：Raw material is prepared, scattered premix, polymerization, blowing recovery defoaming, recovery removing, is crushed, waste water continuous processing.Compared with prior art, advantage is the present invention：Polymeric kettle volume maximizes, and cleaning automation, recovery need not add chemical defoamer, tail gas qualified discharge, sewage disposal serialization, increase substantially production capacity, reduce labor intensity, reduce production cost.
Description
Technical field
The present invention relates to when a kind of device and production method for producing polyvinyl chloride, particularly micro- outstanding newborn method production polychlorostyrene second
Alkene pastes the device and production method of resin.
Background technology
Polyvinyl chloride（PVC）Paste resin as the term suggests be such a resin mainly so that paste forms are made to apply, Ren Menchang
It is referred to as plasticized paste with such a paste, is a kind of unique liquid form of the igelite under rough.Paste resin often by
Emulsion and microsuspending method are made, and its reaction equation is：
nCH2=CHCL——→（CH2-CHCL）n.
For PVC paste resin because granularity is fine, its quality has nonflowing character as talcum powder.PVC paste resin is same
Stable suspension is agitated to form after plasticizer mixing, that is, PVC paste material is made, or makees PVC plasticized pastes, PVC colloidal sols, and
People are exactly used for being processed into end article in this form.It is various according to different product needs, addition during paste producing
Filler, diluent, heat stabilizer, foaming agent and light stabilizer etc..
A kind of development of PVC paste Resin Industry, there is provided the only heated new liquid for being just changed into polrvinyl chloride product
Material.This kind of liquid material configuration is convenient, and stable performance, easy to control, easy to use, product properties is excellent, chemical stability is good,
With certain mechanical strength, easy coloring etc., thus be widely used in artificial leather, flooring laminate, the production of medical, precision instrument and
Elastomeric glove, vinyl toy, soft trade mark, wallpaper, the leaching modeling industry of catering trade（Electronic handle medicine equipment, labour protection hand
Set etc.）, paint, foamed plastic, conveyer belt, the production of automobile decoration etc..
Compared with traditional suspending resin, PVC paste resin has advantages below：
（1）Process equipment is inexpensive；（2）Mould simple cheap；（3）It can be made into F-SP；（4）Foaming is easy；（5）Product
Heated number is few, and can on a small quantity, multi items are produced.
Global paste PVC resin industry is developed with fast speed always, and particularly nearly ten years, production capacity is with yield in jump
Formula increases, and increases in Asia particularly significant.2014, about 5,500,000 tons/year of whole world paste polyvinyl chloride resin aggregated capacity, Chinese production capacity
About 710,000 tons, account for global aggregated capacity 13%.
Preparation method mainly has：
1. emulsion method emulsion polymerization formula mainly has VCM, water, water soluble starter and emulsifying agent.Emulsion polymerization is to stirring
It is required that very strict, initiation is carried out in aqueous phase, and usually used initiator is water soluble persulfates and sulfurous acid
The oxidation-reduction system of salt, reaction speed are relevant with the addition speed and amount of reducing agent.Generally, emulsion polymerization obtains
Serum particle diameter is less than 0.2 μm, in order to reach the purpose of increase serum particle diameter, develops emulsion seeded polymerization, makes serum particle diameter
Increase to 1.0 μm or so.In emulsion polymerization, if the high polymer serum generated is present, control material proportioning and bar
Part, in principle VCM only polymerize on the serum particle generated, without re-forming new particle；This high polymer generated
Serum just looks like crystal seed, therefore referred to as emulsion seeding polymerization.Not only there is rational particle diameter, it is necessary to which there is appropriate particle diameter point
Cloth, it can just obtain the PVC paste resin of function admirable.Emulsifying agent is critically important in emulsion polymerization, and quantity used determines initiator
Population, and main function has been risen to the size of final serum particle.Especially when carrying out seed generation, speed is triggered using height
Rate and low-concentration emulsifier are produced, and serum particle size distribution can be made to narrow.
2. microsuspending method microsuspension polymerization is that a kind of newer method of PVC paste resin is made, its flow is：First by VCM, oil
Stable emulsus is made of the method for mechanical homogenization for soluble initiator, emulsifying agent and water（Particle diameter is at 1.0 μm or so）, then carry out
Polymerization.The excellent flowability of the PVC paste resin produced in this way, emulsifier is few, the heat endurance and water resistant of resin
Property is improved.The production technology need to pay special attention to following influence factor：From suitable compound emulsifying agent and
Grain modifying agent system；The homogenizing of polymerization system component；Mixing speed；The ratio between water and monomer are appropriate.Be in current world wide most
For widely used method.Also it will not go into details herein for some modification methods such as mixing method etc..
Traditional vinyl chloride microsuspension polymerization is divided into chemicals and prepares, polymerize, reclaims blowing, spray drying and crushing, dirt
Several steps such as the semi-automatic processing of water, following aspect deficiency be present：
1）Chemicals is prepared：Dissolving tank and premix groove are smaller, only 6m3.
2）Polymerization：Kettle type is smaller, is up to 48m3；Stir and stirred for oval tubular, remove reaction heat ability.
3）Reclaim blowing：To be reclaimed in kettle, about 4-5 hour of blowing time, low production efficiency are reclaimed；Reclaiming monomer can band
Chemical defoamer need to be added by going out the foam containing serum, because adding this defoamer, can influence to paste resin Downstream processing；Recovery blowing terminates
Afterwards, need to open manhole cover manually high-pressure wash polymeric kettle per kettle, cleaning quality be affected by human factors it is larger, it is dangerous compared with
Height, labor intensity are big.
4）Spray drying and crushing：For negative pressure transportation, fed distance is restricted；Drying tower needs manually high-pressure wash,
Cleaning quality is affected by human factors larger, and dangerous higher, labor intensity is big；VC contents in emission are all in 200ppm
More than, less than toe ring guaranteed request.
5）Sewage disposal：Using semi-automatic handling process, mud cake on filter cloth need to be manually removed.
There are many deficiencies in traditional technique and equipment so that the device production cycle is grown（1 kettle/day）, production capacity is low
（Reclaim blowing and artificial clear kettle takes 8-10 hours）, product quality is bad（Tank diameter is smaller, and machinery emulsification is incomplete, need to add
Add chemical defoamer）, labor intensity is big（Mud cake on manual operation cleaning equipment, artificial removing filter cloth）, and key equipment gathers
Kettle small volume is closed, causes cost to remain high.
The content of the invention
The present invention proposes solution to the problems described above, and provides a kind of dress of micro- outstanding newborn method production PVC paste resin
Put and production method.
The process units of the present invention adopts the following technical scheme that；
A kind of device of micro- outstanding newborn method production PVC paste resin, including storage tank, premix groove, polymeric kettle, blowpit, breast
Glue groove, drying tower, waste water collection tank, storage tank with premix groove be connected, premix groove be connected with polymeric kettle, polymeric kettle respectively with discharging
Groove, gas holder, waste water collection tank connection, waste water collection tank is connected with stripper, and stripper is connected with polymeric kettle, blowpit respectively with
Removing tower, waste water collection tank are connected with defoaming mechanism, and removing tower is connected with latex groove and gas holder respectively, latex groove and drying
Tower is connected, and drying tower is connected with waste water collection tank.
The preferred scheme of above-mentioned process units is：
The port of export of stripper is also connected with equalization basin, and equalization basin is connected with measuring tank, and measuring tank connects with fast mixed groove mixed slowly
Connect, fast mixed groove mixed slowly is connected with neutralization chamber, and neutralization chamber is floating except groove is connected with sand filter and centrifuge respectively with floating except groove is connected.
Premix groove and circulation loop is formed by low-shearing force mulser, porous plate.
Storage tank includes VCM monomers storage tank, desalted water storage tank and hot desalinized water storage tank, VCM monomers storage tank, desalted water storage tank point
Groove is not direct-connected connects with premix, and desalted water storage tank, liquid caustic soda groove, phosphoric acid groove and initiator groove be connecteds with premix groove respectively, dissolving tank and
Premix groove connection.
It is provided with polymeric kettle and concentrates charge pipe and automatic cleaning spraying mechanism, polymeric kettle is that totally-enclosed is jacket structured.
Blowpit passes sequentially through smart wet crushing mill, thin wet crushing mill, serum delivery pump and serum mixing channel and removing
Tower is connected, and the Defoaming machine being connected with gas holder is provided with removing tower.
Drying tower is connected by bag hose with finished product bin.
Dissolving tank is connected with stearic acid tank, emulsifying agent groove and auxiliary groove.
Technical scheme is used by the production technology of the present invention：
Production method, it is controlled by DCS, is carried out as follows：
, raw material prepare：
Auxiliary agent, emulsifying agent and stearic acid are added in dissolving tank and are pre-dissolved with hot water stirs；
, scattered premix：
Desalted water, initiator, phosphoric acid and liquid caustic soda are added in premix groove simultaneously, adds in foregoing dissolving tank and configures
Raw material, then plus VCM monomers, circulation, emulsification in premix groove, material dispersion is delivered into after stable fine droplet
It polymerize in polymeric kettle；
, polymerization：
After afore-mentioned materials are fully entered in polymeric kettle, polymerization is started to warm up, when polymeric kettle pressure rise, reaction temperature reduces
When, polymerisation terminates；When polymeric kettle pressure is down to 0.2-0.6Mpa, discharge of materials to blowpit is reclaimed and stored, wherein
Waste water is unified to be collected in waste water collection tank；
, blowing recovery defoaming：
Reclaimed using negative pressure, when pressure is down to 0.02~0.08Mpa in blowpit, start to reclaim, until in blowpit
Pressure terminates when reaching -400~-700mmHg；
When blowpit carries out negative pressure recovery, steam is passed directly into blowpit and heated up, serum temperature is reached 40
DEG C~80 DEG C, when blowpit pressure reaches setting value, the negative pressure recovery stage of blowpit terminates, and serum is from blowpit delivery pump
It is sent to VC recovery defoamings；
Being carried out in blowpit from when pushing back receipts and negative pressure recovery, system can take the emulsifying agent and serum that foam includes out of,
Defoaming treatment is carried out via dynamic defoaming machine and static Defoaming machine, the serum that is captured is pumped to drying again after returning to blowpit
System is dried；
, recovery removing
Serum is controlled from the frequency conversion of blowpit by flow and is pumped into removing tower；PVC serums add by firing equipment
After heat arrives the temperature of control, it is sent into removing tower tower, is sent to after level removing in dry groove, the chlorine in serum via spray nozzle
Ethylene contents are down to below 300ppm by about 2000ppm；
, dry and classification, crush, malleation conveying：
The serum dried in groove is pumped into spray dryer, bag hose that dried resin enters with air-flow, passes through again
Grader is classified qualified finished product, and coarse granule crushes through pulverizer carry out crushed work again, is delivered to finished product material respectively with malleation
Storehouse, the shaping feeding warehouse for finished product after automatic packaging machine is packed；
, drying tower high pressure cleans automatically：
Spray dryer fortune is using the rinse water pressure control range used in automatic high pressure cleaning equipment：20~35Mpa；
, waste water continuously automatically processes：
The wastewater collection discharged from premix groove, polymeric kettle, blowpit, drying tower is in waste water collection tank, waste water collection tank
In waste water in VC contents in 3000-5000ppm；
Waste water reclaims in waste water after stripper strips and remains VC, and VC contents can be down to below 100ppm, wastewater collection in
Waste water equalization basin imports that air Self-pressurizing agri is floating remove groove after fast mixed slow mixed again, strikes off the sludge of concentration, sludge pumping to centrifugation
Machine, dehydration is collected packed into mud cake after sell it is floating deliver to sand filtration tank except rear waste water and automatically continuously handled, COD contents are down to
Below 200ppm, then deliver to wastewater treatment center processing.
The preferred scheme of production method is：
StepIn, premix groove is in the presence of mulser and porous plate, pre- under 0.3MPa~0.7MPa pressure
Emulsified in mixed groove, make material dispersion into stable fine droplet, effective to control finished product primary particle size, the stream according to DCS establishments
Amount, it is transported in polymeric kettle and polymerize, premixes sump volume scope：90~110m3, the aperture of porous plate is 0.8~2.0mm；Premix
The agitator type of groove is three leaf swept-backs, 2.0~5.0KW/m of agitator stirred volume power bracket3。
StepMiddle polymerization, after discharge of materials to blowpit recovery storage, polymeric kettle inside is carried out quick, safety
Closed high pressure is cleaned automatically, is controlled cleaning step with DCS, is then pressed automatic spray to rinse with closed, enter after rinsing
Row feeding tube cleaning systems, it is rear to carry out the closed automatic spraying of polymeric kettle anti-adhesion agent, wait next polymerization operation.
StepIn, Coarse Aggregate that serum is carried secretly serum by wet type disintegrating machine carries out wet-milling, then by screw pump by serum
From blowpit conveying be pumped into VC recovery defoaming, after be pumped into again serum dry groove, with ensure interval and continuous process
Conversion（Negative pressure discharges）；Steam is passed through the mode of blowpit：It is passed directly into, pressure limit：0.2~0.5Mpa.
StepIn, polymeric kettle volume range：90~110m3；Jacket of polymerization form：Total closed type；Polymeric kettle stirs shape
Formula：Gate stirs；Pressure limit during polymeric kettle discharging：0.2-0.6Mpa；Polymeric kettle cleaning way：Closed high pressure is automatically clear
Wash, pressure limit：25~35Mpa；Polymeric kettle is sprayed mode：Automatic cleaning, pressure limit are pressed in closed：2.5~4.0
MPa；Close kettle anti-adhesion agent spraying method：Closed automatic spraying.
PVC serums are sent into removing tower tower after firing equipment is heated to the temperature of control via spray nozzle, through the
The PVC serums of one-level removing tower removing are from bottom of towe pipeline via being pumped into second level removing tower；Add second level removing tower it
Before, PVC serums are heated to control temperature by firing equipment with steam；After two-stage removes, content of vinylchloride in serum by
About 2000ppm is down to below 300ppm；The residence time of serum is 3~6 hours；Serum steam mixer, control temperature model
Enclose：50~80 DEG C；Vacuum degree control scope in removing tower：- 400~-700mmHg.
StepDescribed in spray drying and classification, crushing, the malleation discharge pressure control range of malleation supplying step：
3000-5000mmH2O。
StepMiddle waste water, which continuously automatically processes, mainly to be reclaimed VC in waste water and removes SS；Steam injection mode：From waste water
Collect trench bottom injection；The operating condition of steam：80-98 DEG C of temperature, pressure -400~-700mmHg；Mixed revolution control model soon
Enclose：80~100 revs/min；Slowly mixed revolution control range：30~50 revs/min.
Using the present invention of above-mentioned technical proposal, advantage is：Polymeric kettle volume maximizes, and cleaning automation, recovery need not
Chemical defoamer is added, tail gas qualified discharge, sewage disposal serialization, increases substantially production capacity, reduces labor intensity, drop
Low production cost.
Brief description of the drawings：
Fig. 1 is the production technological process of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and the present invention is described in detail in embodiment：
A kind of device and production method of micro- outstanding newborn method production PVC paste resin, referring to accompanying drawing 1, in figure：Sand filter
1st, breast is except groove 2, neutralization chamber 3, fast mixed groove 4 mixed slowly, measuring tank 5, equalization basin 6, centrifuge 7, stripper 8, the first vavuum pump 9, useless
Water collecting groove 10, low scissors power mulser 11, porous plate 12, VCM monomers storage tank 13, desalted water storage tank 14, hot desalinized water storage tank
15th, stearic acid 16, emulsifying agent 17, auxiliary agent 18, dissolving tank 19, liquid caustic soda groove 20, phosphoric acid 21, initiator 22, automatic cleaning and spray
Mechanism 23, concentrate charge pipe 24, premix groove 25, polymeric kettle 26, dynamic defoaming machine 27, thick wet crushing mill 28, thin case of wet attrition
Machine 29, serum delivery pump 30, dynamic defoaming machine 31, static Defoaming machine 32, the second vavuum pump 33, gas holder 34, the 3rd vavuum pump 35,
First steam separating tank 36A, the first serum mixing channel 37A, the first Defoaming machine 38A, the first removing tower A 39, the separation of the second steam
Groove 37B, the second serum mixing channel 37B, the second Defoaming machine 38B, the second removing tower 39B, latex groove 40, serum constant displacement pump 41,
42, one sections of bag hoses 43 of drying tower, section machine 44, two sections of collection powder tanks 45,46, two sections of bag hose A47 of Dry-crusher, two sections of bags
Filter B48, finished product bin A49, finished product bin B 50, automatic packaging system A51, automatic packaging system B52, agitator 53.
Storage tank includes VCM monomers storage tank 13, desalted water storage tank 14 and hot desalinized water storage tank 15；VCM monomers storage tank 13, desalination
Groove 25 is direct-connected connects with premix respectively for water storage tank 14, desalted water storage tank 14, liquid caustic soda groove 20, phosphoric acid groove 21 and initiator groove 22 respectively with
Premix groove 25 is connected, and dissolving tank 19 is connected with premix groove 25.
Premix groove 25 is connected with polymeric kettle 26, and polymeric kettle 26 connects with blowpit 27, gas holder 34, waste water collection tank 10 respectively
Connect, waste water collection tank 10 is connected with stripper 8, and stripper 8 is connected with polymeric kettle 26 and steam chest 34 respectively, blowpit 27 respectively with
Removing tower, waste water collection tank 10 are connected with defoaming mechanism, and removing tower is connected with latex groove 40 and gas holder 34 respectively, latex groove
40 are connected with drying tower 42, and drying tower 42 is connected with waste water collection tank 10；The slant setting of blowpit 27, with horizontal plane exist 5 to
10 degree of angles.
Removing tower is provided with two, is the first removing tower 39A and the second removing tower 39B, the first removing tower 39A and respectively
Two removing tower 39B connections, the second removing tower 39B are connected with milk glue groove 40.
Defoaming mechanism is made up of dynamic defoaming machine 31 and static Defoaming machine 32, and dynamic defoaming machine 31 connects with static Defoaming machine 32
Connect, static Defoaming machine is connected with blowpit 27.
The port of export of stripper 8 is also connected with equalization basin 6, and equalization basin 6 is connected with measuring tank 5, and measuring tank 5 mixes slow mix with fast
Groove 4 is connected, and fast mixed groove 4 mixed slowly is connected with neutralization chamber 3, neutralization chamber 3 with floating except groove 2 is connected, it is floating remove groove 2 respectively with sand filter 1 and
Centrifuge 7 connects.
Premix groove 25 and circulation loop is formed by low-shearing force mulser 11, porous plate 12；Collection is provided with polymeric kettle 26
Middle charge pipe 24 and automatic cleaning spraying mechanism 23, the lower end of polymeric kettle 26 are equipped with agitator 53, and polymeric kettle 26 is totally-enclosed chuck
Structure.
Blowpit 27 passes sequentially through smart wet crushing mill 28, thin wet crushing mill 29, the serum of serum delivery pump 30 and first
Mixing channel 37A is connected with the first removing tower 39A, and the first Defoaming machine being connected with gas holder 34 is provided with the first removing tower 39A
38A；The first steam separating tank 36A is provided with first serum mixing channel 37A.First removing tower 39A and the second serum mixing channel
37B connections, the second serum mixing channel 37B are connected with the second removing tower 39B, and the second vapour is provided with the second milk mixing channel 37B
Separating tank 36B.
Drying tower 42 is connected by one section of bag hose 43 with one section of collection powder tank 44, and one section of collection powder tank 44 is connected with grader,
Grader is connected with two sections of bag hose A47；Two sections of bag hose A47 are connected with finished product bin A49；Finished product bin A49 and automatic bag
The A51 connections of dress system.
Grader is also connected with two sections of collection powder tanks 45, and two sections of collection powder tanks 45 are connected with Dry-crusher 46, Dry-crusher
46 are connected with two sections of bag hose B48；Two sections of bag hose B48 are connected with finished product bin B50；Finished product bin B50 and automatic packaging system
System B52 connections.
Dissolving tank 19 is connected with stearic acid tank 16, emulsifying agent groove 17 and auxiliary groove 18.
Production method, embodiment 1：
The present embodiment is based under security consideration, and the reaction of polymeric kettle 29 uses in normal service is not turned on manhole cover
Airtight connection mode is carried out, and so as to improve the quality of product and production efficiency and safe operation, whole production process is by DCS
Control, is carried out as follows：
（One）, raw material prepare：
By auxiliary agent, emulsifying agent and stearic acid（This three's solid-state or liquid can be with）By 3 ~ 5: 4~6 :1 volume
Ratio is added in dissolving tank 19 and is pre-dissolved with hot water stirs, and auxiliary agent is 75 ~ 90Kg, the volume of the volume of dissolving tank 19 15~
25m3, dissolving tank hot water temperature's scope：55 DEG C~75 DEG C.
（Two）, scattered premix：
35~45 cubic metres of desalted water, initiator, phosphoric acid and liquid caustic soda are pressed 1300 ~ 1500: 1~2 : 1~3 : 1~3
Volume ratio simultaneously add premix groove 25 in, add in foregoing dissolving tank 25 raw material configured, then add VCM monomers 15 ~
36 tons, circulation, emulsification in premix groove 25, premix groove 25 is in the presence of low-shearing force mulser 11 and porous plate 12, thing
Material emulsifies under 0.3MPa~0.7MPa pressure in groove 25 is premixed, and makes material dispersion into stable about 0.2 ~ 1 micron
Fine droplet, it is effective to control finished product primary particle size, according to the flow of DCS establishments, it is transported in polymeric kettle 26 and polymerize, premixes groove
25 volume ranges：90~110m3, the aperture of porous plate 12 is 0.8~2.0mm.
The agitator type of premix groove 25 is three leaf swept-backs, 2.0~5.0Kw/m of agitator stirred volume power bracket3。
Paste in production of resins, emulsifying material volume flow is sufficiently high, could realize that low sheraing emulsifies, volume during emulsification
4~8 times of range of flow.
The scattered pre-mixing process, substantially reduces emulsification times, makes the drop after emulsification finer and smoother, particle diameter distribution cloth is more
Add it is uniform, regular, meet paste resin following process production technology requirement, so as to improve product quality.
The charging that desalted water is used in all kinds of grooves and the cleaning of kettle and scattered pre-mixing process is used；35~45 cubes of desalted water
Rice；Pressure value：About 4Kg；Time：About 10 minutes.
（Three）, polymerization：
After afore-mentioned materials are fully entered in polymeric kettle 26, polymerization is started to warm up, because polymerization exotherm reacts, polymeric kettle 26 is adopted
With total closed type chuck and stirring-type structure, by reaction heat and removal.
When pressure rise to 0.5 ~ 0.6MPa, the reaction temperature of polymeric kettle 26 reduces（Reduce about 0.5 ~ 1.5 degree）When, polymerization
Reaction terminates；When polymeric kettle pressure is down to 0.2~0.6Mpa, discharge of materials to blowpit 27 is reclaimed into storage, wherein waste water
It is unified to collect in waste water collection tank 10.
The volume range of polymeric kettle 26：90~110m3；The chuck form of polymeric kettle 26：Total closed type；Polymeric kettle 26 stirs shape
Formula：Gate stirs；Pressure limit during 26 discharging of polymeric kettle：0.2~0.6Mpa；The cleaning way of polymeric kettle 26：Closed high pressure is certainly
Dynamic cleaning, pressure limit：25~35Mpa；Polymeric kettle 26 is sprayed mode：Automatic cleaning, pressure limit are pressed in closed：
2.5~4.0 MPa；The anti-adhesion agent spraying method of polymeric kettle 26：Closed automatic spraying.
After discharge of materials is reclaimed into storage to blowpit 27, it is high that quick, safety closed is carried out to the inside of polymeric kettle 26
The automatic cleaning of pressure, controls cleaning step with DCS, then presses automatic spray to rinse with closed, carry out charge pipe after rinsing
Road cleaning systems, it is rear to carry out the closed automatic spraying of the anti-adhesion agent of polymeric kettle 26, wait next polymerization operation.
（Four）, blowing recovery defoaming：
Reclaimed using negative pressure, when pressure is down to 0.02~0.08Mpa in blowpit 27, start to reclaim, until blowpit
Pressure reaches -400~-700mmHg in 27（About -0.004~-0.007Mpa）When terminate.
In blowpit 27（27 inclined placement of blowpit, the about angle horizontal by 5~10 degree）；Carry out certainly
Pressure（By self gravitation）And during negative pressure recovery, steam is passed directly into blowpit 27 and heated up, pressure limit：0.2~
0.5Mpa。
Serum temperature is set to reach 40 DEG C~80 DEG C, when the pressure of blowpit 27 reaches setting value, the negative pressure of blowpit 27 is returned
The receipts stage terminates, and serum is pumped into removing tower recovery defoaming from the conveying of blowpit 27.
Carried out in blowpit 27 from when pushing back receipts and negative pressure recovery, system can take the emulsifying agent and breast that foam includes out of
Slurry, defoaming treatment is carried out via dynamic rotating machine 31 and static Defoaming machine 32,（Dynamic defoaming machine 31, specification EM-431, Kunshan is forever
Win Products；Static Defoaming machine 32, model：EC-431）.The serum that is captured is pumped to drying again after returning to blowpit 27
System is dried.
The Coarse Aggregate that serum is carried secretly serum by thick wet type disintegrating machine carries out wet-milling, then by screw pump by serum from discharging
Groove 27 by be pumped into VC take off tower recovery defoaming, after be pumped into again serum dry groove 40, with ensure interval and continuous processing mistake
The conversion of journey（Negative pressure discharges）.
（Four）, recovery removing
Serum is controlled from the frequency conversion of blowpit 27 by flow and is pumped into removing tower；PVC serums pass through firing equipment
Be heated to control temperature after, via spray nozzle be sent into removing tower tower in, through the first order removing tower 39A removing PVC serums from
Bottom of towe pipeline is via being pumped into the removing tower 39B of the second level；Before second level removing tower 39B is added, PVC serums are by adding
Heat sets reserve steam and is heated to control 50~80 DEG C of temperature；The residence time of serum is 3~6 hours；Serum steam mixer,
Vacuum degree control is in -400~-700 millimetress of mercury in removing tower.It is sent to after two-stage removes, after removing in dry groove 40,
Content of vinylchloride in serum is down to below 300ppm by about 2000ppm.
（Five）, dry and classification, crush, malleation conveying：
The serum dried in groove 40 is pumped into atomizing drier 42, and the bag that dried resin enters with air-flow is filtered
Device, qualified finished product is classified through grader again, coarse granule is crushed through pulverizer carry out crushed work again, is delivered to respectively with malleation
Finished product bin, the shaping feeding warehouse for finished product after automatic packaging machine is packed.Spray drying and classification, crush, malleation supplying step
Malleation discharge pressure is controlled in 3000~5000mmH2O.Automatic packaging：Using open type or port type automatic packaging system.
Spray drying and classification, crushing, malleation supplying step by using the present invention, fed distance are left up to 200m
The right side, the integral arrangement of dry, packaging and finished room can be made more flexible.
（Six）, drying tower high pressure cleans automatically：
Atomizing drier 42 is run can be attached in tower wall through slurry after a period of time, can drop and make in producing
Quality is influenceed into pollution paste resin finished product, can be effectively by tower via automatic high pressure cleaning equipment so must be set a period of time
Wall cleans up.
Rinse water pressure control range used in the automatic high pressure cleaning equipment of the automatic cleaning step of drying tower high pressure：20~
35Mpa。
Cleaned automatically by high pressure, labor intensity can be greatly lowered, improve final product quality and yield rate.
（Seven）, waste water continuously automatically processes：Mainly reclaim VC in waste water and remove SS.Steam injection mode：From waste water
The bottom of collecting tank 10 is injected；The operating condition of steam：80-98 DEG C of temperature, the mmHg of pressure -400~-700；Mixed revolution control soon
Scope：80~100 revs/min；Slowly mixed revolution control range：30~50 revs/min.
From premix groove 25, polymeric kettle 26, blowpit 27, drying tower 42 discharge wastewater collection in waste water collection tank 10,
VC contents are in 3000-5000ppm in waste water in waste water collection tank 10.
Waste water reclaims in waste water after the stripping of stripper 8 and remains VC, VC contents can be down to below 100ppm, wastewater collection
In waste water equalization basin 6（COD contents 2000-3000ppm, SS content 3000-5000ppm）, then imported after fast mixed groove 4 mixed slowly
Air Self-pressurizing agri is floating to remove groove 2, strikes off the sludge of concentration, sludge pumping to centrifuge 7, and dehydration goes out after collecting into mud cake packaging
Sell, floating to deliver to sand filter 1 except rear waste water and automatically continuously handled, COD contents are down to below 200ppm, then deliver to wastewater treatment
Center processing；The a whole set of continuous automated processing system of waste water is controlled by DCS, reduces labor intensity.
Embodiment 2：
The present embodiment is based under security consideration, and the reaction of polymeric kettle 29 uses in normal service is not turned on manhole cover
Airtight connection mode is carried out, and so as to improve the quality of product and production efficiency and safe operation, whole production process is by DCS
Control, is carried out as follows：
（One）, raw material prepare：
By auxiliary agent, emulsifying agent and stearic acid（This three's solid-state or liquid can be with）By 3: 4 :1 volume ratio
Add in dissolving tank 19 and be pre-dissolved with hot water stirs, auxiliary agent 75Kg, the volume 15m of the volume of dissolving tank 193, dissolving tank hot water temperature
Spend scope：55℃.
（Two）, scattered premix：
35 cubic metres of hot desalinized water, initiator, phosphoric acid and liquid caustic soda are pressed 1300: 1 : 1 :1 volume ratio is simultaneously
Add in premix groove 25, add in foregoing dissolving tank 25 raw material configured, then add 15 tons of VCM monomers, in premix groove 25
Interior circulation, emulsification, premix groove 25 in the presence of low-shearing force mulser 11 and porous plate 12, material 0.3MPa~
Emulsified under 0.7MPa pressure in groove 25 is premixed, make material dispersion into about 0.2 ~ 1 micron stable of fine droplet, effectively
Control finished product primary particle size, according to the flow of DCS establishments, be transported in polymeric kettle 26 and polymerize, premix the volume range of groove 25：
90m3, the aperture of porous plate 12 is 0.8~2.0mm.
The agitator type of premix groove 25 is three leaf swept-backs, 2.0~5.0Kw/m of agitator stirred volume power bracket3。
Paste in production of resins, emulsifying material volume flow is sufficiently high, could realize that low sheraing emulsifies, volume during emulsification
4~8 times of range of flow.
The scattered pre-mixing process, substantially reduces emulsification times, makes the drop after emulsification finer and smoother, particle diameter distribution cloth is more
Add uniform, regular, the requirement of paste resin following process production work is met, so as to improve product quality.
（Three）, polymerization：
After afore-mentioned materials are fully entered in polymeric kettle 26, polymerization is started to warm up, because polymerization exotherm reacts, polymeric kettle uses
Total closed type chuck and stirring-type structure, by reaction heat and removal.
When pressure rise to 0.5 ~ 0.6MPa, the reaction temperature of polymeric kettle 26 reduces（Reduce about 0.5 ~ 1.5 degree）When, polymerization
Reaction terminates；When polymeric kettle pressure is down to 0.2~0.6Mpa, discharge of materials to blowpit 27 is reclaimed into storage, wherein waste water
It is unified to collect in waste water collection tank 10.
The volume range of polymeric kettle 26：90m3；The chuck form of polymeric kettle 26：Total closed type；The whipped form of polymeric kettle 26：Gate
Stirring；Pressure limit during 26 discharging of polymeric kettle：0.2~0.6Mpa；The cleaning way of polymeric kettle 26：Closed high pressure is cleaned automatically,
Pressure limit：25~35Mpa；Polymeric kettle 26 is sprayed mode：Automatic cleaning, pressure limit are pressed in closed：2.5~4.0
MPa；Close kettle anti-adhesion agent spraying method：Closed automatic spraying.
After discharge of materials is reclaimed into storage to blowpit 27, it is high that quick, safety closed is carried out to the inside of polymeric kettle 26
The automatic cleaning of pressure, controls cleaning step with DCS, then presses automatic spray to rinse with closed, carry out charge pipe after rinsing
Road cleaning systems, it is rear to carry out the closed automatic spraying of the anti-adhesion agent of polymeric kettle 26, wait next polymerization operation.
（Four）, blowing recovery defoaming：
Reclaimed using negative pressure, when pressure is down to 0.02~0.08Mpa in blowpit 27, start to reclaim, until blowpit
Terminate when pressure reaches -400~-700 mmHg in 27.
In blowpit 27（27 inclined placement of blowpit, the about angle horizontal by 5~10 degree）；Carry out certainly
Pressure（By self gravitation）And during negative pressure recovery, steam is passed directly into blowpit 27 and heated up, pressure limit：0.2~
0.5Mpa。
Serum temperature is set to reach 40 DEG C~80 DEG C, when the pressure of blowpit 27 reaches setting value, the negative pressure of blowpit 27 is returned
The receipts stage terminates, and serum is pumped into removing tower recovery defoaming from the conveying of blowpit 27.
Carried out in blowpit 27 from when pushing back receipts and negative pressure recovery, system can take the emulsifying agent and breast that foam includes out of
Slurry, defoaming treatment is carried out via dynamic rotating machine 31 and static Defoaming machine 32,（Dynamic defoaming machine 31, specification EM-431, Kunshan is forever
Win Products；Static Defoaming machine 32, model：EC-431）.The serum that is captured is pumped to drying again after returning to blowpit 27
System is dried.
The Coarse Aggregate that serum is carried secretly serum by thick wet type disintegrating machine carries out wet-milling, then by screw pump by serum from discharging
Groove 27 by be pumped into VC take off tower recovery defoaming, after be pumped into again serum dry groove 40, with ensure interval and continuous processing mistake
The conversion of journey（Negative pressure discharges）.
（Four）, recovery removing
Serum is controlled from the frequency conversion of blowpit 27 by flow and is pumped into removing tower；PVC serums pass through firing equipment
Be heated to control temperature after, via spray nozzle be sent into removing tower tower in, through the first order removing tower 39A removing PVC serums from
Bottom of towe pipeline is via being pumped into the removing tower 39B of the second level；Before second level removing tower 39B is added, PVC serums are by adding
Heat sets reserve steam and is heated to control 50~80 DEG C of temperature；The residence time of serum is 3~6 hours；Serum steam mixer,
Vacuum degree control is in -400~-700mmHg in removing tower（About -0.053~-0.093Mpa）.After two-stage removes, quilt after removing
Deliver in dry groove 40, the content of vinylchloride in serum is down to below 300ppm by about 2000ppm.
（Five）, dry and classification, crush, malleation conveying：
The serum dried in groove 40 is pumped into atomizing drier 42, and the bag that dried resin enters with air-flow is filtered
Device, qualified finished product is classified through grader again, coarse granule is crushed through pulverizer carry out crushed work again, is delivered to respectively with malleation
Finished product bin, the shaping feeding warehouse for finished product after automatic packaging machine is packed.Spray drying and classification, crush, malleation supplying step
Malleation discharge pressure is controlled in 3000~5000mmH2O（0.03~0.05Mpa）.Automatic packaging：Using open type or port type
Automatic packaging system.
Spray drying and classification, crushing, malleation supplying step by using the present invention, fed distance are left up to 200m
The right side, the integral arrangement of dry, packaging and finished room can be made more flexible.
（Six）, drying tower high pressure cleans automatically：
Atomizing drier 42 is run can be attached in tower wall through slurry after a period of time, can drop and make in producing
Quality is influenceed into pollution paste resin finished product, can be effectively by tower via automatic high pressure cleaning equipment so must be set a period of time
Wall cleans up.
Rinse water pressure control range used in the automatic high pressure cleaning equipment of the automatic cleaning step of drying tower high pressure：20~
35Mpa。
Cleaned automatically by high pressure, labor intensity can be greatly lowered, improve final product quality and yield rate.
（Seven）, waste water continuously automatically processes：Mainly reclaim VC in waste water and remove SS.Steam injection mode：From waste water
The bottom of collecting tank 10 is injected；The operating condition of steam：80-98 DEG C of temperature, the mmHg of pressure -400~-700；Mixed revolution control soon
Scope：80~100 revs/min；Slowly mixed revolution control range：30~50 revs/min.
From premix groove 25, polymeric kettle 26, blowpit 27, drying tower 42 discharge wastewater collection in waste water collection tank 10,
VC contents are in 3000~5000ppm in waste water in waste water collection tank 10.
Waste water reclaims in waste water after the stripping of stripper 8 and remains VC, VC contents can be down to below 100ppm, wastewater collection
In waste water equalization basin 6（COD contents 2000-3000ppm, SS content 3000-5000ppm）, then imported after fast mixed groove 4 mixed slowly
Air Self-pressurizing agri is floating to remove groove 2, strikes off the sludge of concentration, sludge pumping to centrifuge 7, and dehydration goes out after collecting into mud cake packaging
Sell, floating to deliver to sand filter 1 except rear waste water and automatically continuously handled, COD contents are down to below 200ppm, then deliver to wastewater treatment
Center processing；The a whole set of continuous automated processing system of waste water is controlled by DCS, reduces labor intensity.
The technological process carried out the invention is not restricted to the parameters value cited by above-described embodiment, as long as using the dress
Put and the technological process carry out microsuspending method production PVC paste resin method, equal apparent for the present invention protection model
Within enclosing.
Claims (8)
1. a kind of production method of micro- outstanding newborn method production PVC paste resin, its device includes storage tank, premix groove, polymeric kettle,
Blowpit, latex groove, drying tower, waste water collection tank, storage tank are connected with premix groove, and premix groove is connected with polymeric kettle, polymeric kettle
It is connected respectively with blowpit, gas holder, waste water collection tank, waste water collection tank is connected with stripper, and stripper is connected with polymeric kettle, is unloaded
Hopper is connected with removing tower, waste water collection tank and defoaming mechanism respectively, and removing tower is connected with latex groove and gas holder respectively, latex
Groove is connected with drying tower, and drying tower is connected with waste water collection tank；The port of export of stripper is also connected with equalization basin, equalization basin with
Measuring tank is connected, and measuring tank be connected with fast mixed groove mixed slowly, and the fast mixed groove that mixes slowly is connected with neutralization chamber, neutralization chamber with floating except groove is connected,
Float except groove is connected with sand filter and centrifuge respectively；Premix groove and circulation loop is formed by low-shearing force mulser, porous plate；Storage
Groove includes VCM monomers storage tank, desalted water storage tank and hot desalinized water storage tank, and VCM monomers storage tank, desalted water storage tank are respectively with premixing groove
Direct-connected to connect, desalted water storage tank, liquid caustic soda groove, phosphoric acid groove and initiator groove are connected with premix groove respectively, and dissolving tank is connected with premix groove；
It is provided with polymeric kettle and concentrates charge pipe and automatic cleaning spraying mechanism, polymeric kettle is that totally-enclosed is jacket structured；Blowpit is successively
It is connected with removing tower by smart wet crushing mill, thin wet crushing mill, serum delivery pump and serum mixing channel, is set in removing tower
There is the Defoaming machine being connected with gas holder；Drying tower is connected by bag hose with finished product bin；Dissolving tank and stearic acid tank, emulsifying agent groove
Connected with auxiliary groove；It is characterized in that：It is controlled by DCS, is carried out as follows：
, raw material prepare：
Auxiliary agent, emulsifying agent and stearic acid are added in dissolving tank and are pre-dissolved with hot water stirs；
, scattered premix：
Desalted water, initiator, phosphoric acid and liquid caustic soda are added in premix groove simultaneously, add in foregoing dissolving tank the original configured
Then plus VCM monomers material, circulation, emulsification in premix groove, material dispersion is made to be delivered to polymerization into after stable fine droplet
It polymerize in kettle；
, polymerization：
After afore-mentioned materials are fully entered in polymeric kettle, polymerization is started to warm up, when polymeric kettle pressure reduces, and reaction temperature reduces,
Polymerisation terminates；When polymeric kettle pressure is down to 0.2-0.6MPa, discharge of materials to blowpit is reclaimed and stored, wherein waste water
It is unified to collect in waste water collection tank；
, blowing recovery defoaming：
Reclaimed using negative pressure, when pressure is down to 0.02~0.08MPa in blowpit, start to reclaim, until pressure in blowpit
Terminate when reaching -400~-700mmHg；
Blowpit carry out negative pressure recovery when, steam is passed directly into blowpit and heated up, make serum temperature reach 40 DEG C~
80 DEG C, when blowpit pressure reaches setting value, the negative pressure recovery stage of blowpit terminates, and serum is pumped into from blowpit conveying
VC recovery defoamings；
Being carried out in blowpit from when pushing back receipts and negative pressure recovery, system can take the emulsifying agent and serum that foam includes out of, via
Dynamic defoaming machine and static Defoaming machine carry out defoaming treatment, and the serum that is captured is pumped to drying system again after returning to blowpit
It is dried；
, recovery removing
Serum is controlled from the frequency conversion of blowpit by flow and is pumped into removing tower；PVC serums are heated to by firing equipment
After the temperature of control, it is sent into removing tower tower, is sent to after level removing in dry groove, the vinyl chloride in serum via spray nozzle
Content is down to below 300ppm by 2000ppm；
, dry and classification, crush, malleation conveying：
Dry the serum in groove and be pumped into spray dryer, dried resin enters bag hose, again through grader with air-flow
Qualified finished product is classified, coarse granule crushes through pulverizer carry out crushed work again, is delivered to finished product bin respectively with malleation, through certainly
Warehouse for finished product is sent into shaping after dynamic packing machine packaging；
, drying tower high pressure cleans automatically：
Spray dryer is using the rinse water pressure control range used in automatic high pressure cleaning equipment：20~35MPa；
, waste water continuously automatically processes：
The wastewater collection discharged from premix groove, polymeric kettle, blowpit, drying tower is in waste water collection tank, in waste water collection tank
VC contents are in 3000-5000ppm in waste water；
Waste water reclaims in waste water after stripper strips and remains VC, VC contents can be down to below 100ppm, and wastewater collection is in waste water
Equalization basin imports that air Self-pressurizing agri is floating remove groove after fast mixed slow mixed again, strikes off the sludge of concentration, sludge pumping to centrifuge is de-
Water is collected packed into mud cake after sell it is floating deliver to sand filtration tank except rear waste water and automatically continuously handled, COD contents are down to 200ppm
Hereinafter, then wastewater treatment center processing is delivered to.
2. production method according to claim 1, it is characterised in that：StepIn, premix groove is in mulser and porous plate
In the presence of, emulsified under 0.3MPa~0.7MPa pressure in groove is premixed, material dispersion is had into stable fine droplet
The control finished product primary particle size of effect, according to the flow of DCS establishments, it is transported in polymeric kettle and polymerize, premix sump volume scope：90~
110m3, the aperture of porous plate is 0.8~2.0mm；
The agitator type of premix groove is three leaf swept-backs, 2.0~5.0KW/m of agitator stirred volume power bracket3。
3. production method according to claim 1, it is characterised in that：StepMiddle polymerization, discharge of materials to blowpit is returned
Store up after depositing, quick, safety closed high pressure is carried out to polymeric kettle inside and is cleaned automatically, cleaning step is controlled with DCS, then
Press automatic spray to rinse with closed, carry out feeding tube cleaning systems after rinsing, rear progress polymeric kettle anti-adhesion agent is closed
Automatic spraying, waits next polymerization operation.
4. production method according to claim 1, it is characterised in that：StepIn, serum is by wet crushing mill by serum
The Coarse Aggregate of entrainment carries out wet-milling, then serum is pumped into VC recovery defoamings from blowpit conveying by screw pump, after be pumped into again
Serum dries groove, to ensure the conversion of interval and continuous process；Steam is passed through the mode of blowpit：It is passed directly into, presses
Power scope：0.2~0.5MPa.
5. production method according to claim 1, it is characterised in that：StepIn, polymeric kettle volume range：90~110m3；
Jacket of polymerization form：Total closed type；Polymeric kettle whipped form：Gate stirs；Pressure limit during polymeric kettle discharging：0.2-
0.6MPa；Polymeric kettle cleaning way：Closed high pressure is cleaned automatically, pressure limit：25~35MPa；Polymeric kettle spray irrigation side
Formula：Automatic cleaning, pressure limit are pressed in closed：2.5~4.0 MPa；Close kettle anti-adhesion agent spraying method：Closed automatic spraying.
6. production method according to claim 1, it is characterised in that：PVC serums are heated to control by firing equipment
After temperature, it is sent into via spray nozzle in removing tower tower, the PVC serums through the removing of first order removing tower are from bottom of towe pipeline via pumping
Enter second level removing tower；Before second level removing tower is added, PVC serums are heated to control temperature by firing equipment with steam
Degree；After two-stage removes, the content of vinylchloride in serum is down to below 300ppm by 2000ppm；The residence time of serum is 3
~6 hours；Serum steam mixer, control temperature range：50~80 DEG C；Vacuum degree control scope in removing tower：-400
~-700mmHg.
7. production method according to claim 1, it is characterised in that：StepDescribed in spray drying and classification, powder
Broken, malleation supplying step malleation discharge pressure control range：3000~5000mmH2O。
8. production method according to claim 1, it is characterised in that：StepMiddle waste water, which continuously automatically processes, mainly to return
Receive VC in waste water and remove SS；Steam injection mode：Injected from wastewater collection trench bottom；The operating condition of steam：Temperature 80-98
DEG C, pressure -400~-700mmHg；Mixed revolution control range soon：80~100 revs/min；Slowly mixed revolution control range：30~50
Rev/min.
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| CN106317269B (en) * | 2016-10-18 | 2018-08-21 | 唐山三友氯碱有限责任公司 | The device and method of vinyl chloride monomer are recycled in microsuspending method PVC paste resin production process |
| CN107141386A (en) * | 2017-06-16 | 2017-09-08 | 唐山三友氯碱有限责任公司 | A kind of method for producing PVC paste resin and reaction retracting device |
| CN110954433B (en) * | 2019-12-19 | 2022-10-14 | 沈阳化工股份有限公司 | Method for testing oil absorption rate of PVC paste resin |
| CN113136000B (en) * | 2021-03-16 | 2022-12-30 | 天津市滨海新区众友缘科技发展有限公司 | Polyvinyl chloride paste resin micro-suspension polymerization method |
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| CN102368067A (en) * | 2011-11-27 | 2012-03-07 | 天津渤天化工有限责任公司 | Testing device and method for production of paste resin with microsuspension method |
| CN203763915U (en) * | 2014-03-08 | 2014-08-13 | 新疆天业（集团）有限公司 | Mechanical polyvinyl chloride paste resin defoaming device |
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| CN102368067A (en) * | 2011-11-27 | 2012-03-07 | 天津渤天化工有限责任公司 | Testing device and method for production of paste resin with microsuspension method |
| CN203763915U (en) * | 2014-03-08 | 2014-08-13 | 新疆天业（集团）有限公司 | Mechanical polyvinyl chloride paste resin defoaming device |
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