CN1314421A - Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process - Google Patents
Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process Download PDFInfo
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Abstract
The medium size polymerizing still includes still body with length-to-diameter ratio of 1.6-1.95 and volume of 40-60 cubic meter, top entering drive mechanism, two-layer three-blade sweepback agitator, and half-pipe coil cooling jacket. It has high heat transfer effect and high yield of unit volume and is especially suitable for small and medium sized enterprises.
Description
The present invention relates to the medium-sized polymeric kettle of suspension polymerization of VC and adopt the method for this polymeric kettle polymerizing vinyl chloride, specifically, the present invention relates to have the 40-60m of improved three leaf swept-back agitators
3Polymeric kettle and adopt the method for this polymeric kettle suspension polymerization vinylchlorid.
In the production process of polyvinyl chloride, exist problems such as sticking still, product particle is inhomogeneous, heat transfer is poor always, have a strong impact on the quality of polyvinyl chloride product; Particularly sticking still is an open question all the time in the Production of PVC, in the general Production of PVC process, all will clean still after the polymerization each time, influences the performance of polymeric kettle throughput.And the generation of the problems referred to above, remove have with polymerization technique outside the Pass, also with the structure of polymeric kettle, comprise that the design of support equipment is relevant.
In the Production of PVC process, polymeric kettle is main production unit, and the quality of its technical feature directly has influence on the economy etc. of output, quality and the operation of polyvinyl chloride.At present, the home-made pvc polymerizer has only 30m
3, 13.5m
3And 7m
3Several little still types.These small-sized polymerization kettle unit volume output are little, the energy consumption height, and also counter investment is big, and production efficiency is low, has been superseded gesture.The eighties, China once developed 80m
3Large-scale polymeric kettle, but because structure and other various reasons of still itself fails to promote the use of, the polymeric kettle of external use is based on large-scale at present, for example U.S. Gu Te Ritchie 70m
3Polymeric kettle, the Japanese 127m of SHIN-ETSU HANTOTAI
3Polymeric kettle, the 200m of German sweat you this
3The 105m in polymeric kettle and Europe
3Polymeric kettle etc.These large-scale polymeric kettle production efficiency height, economic performance is good, but its technical requirements and equipment introduction expense are all very high, and only be applicable to the production of large-lot producer.Along with the polyvinyl chloride industrial expansion, the chloroethylene polymerization still also towards most economical, production efficiency is high, construction cost and maintenance cost is low, good product quality, direction that output is big develop.Up to the present, the polyvinyl chloride annual production of China is many with middle-size and small-size production plant about 1,900,000 tonnages.According to investigations, can satisfy the polymeric kettle of China medium and small sized enterprises technological transformation needs, be a kind of between 40m
3With 60m
3Between dynamical medium-sized polymeric kettle.This polymeric kettle can not be that prototype is directly dwindled or amplified and obtains with existing big still or little still, must develop from the production technique of polyvinyl chloride.The polymeric kettle of this model does not still have report at present both at home and abroad.
The general polymerization still adopts the cooling of cooling jacket form, conventional jacket, spiral stream guidance type chuck, semicanal spiral chuck are arranged, conventional jacket has no longer been adopted in the design of polymeric kettle at present, because water coolant is entered by the chuck end opening, through the chuck ring go straight up to and on, overflow by suitable for reading, flow velocity is very low, turbulent extent is not enough, the cooling performance extreme difference.Though adopting the spiral chuck to conduct heat makes moderate progress, processing preferably under the situation, can obtain big flow velocity (2-3m/s), thereby improve heat-transfer effect significantly, it is relatively good ideal method of cooling, but because of being subject to processing the restriction of manufacturing, water coolant is walked " short circuit " easily reduces heat transfer coefficient, so the method for cooling of polymeric kettle also haves much room for improvement.
The purpose of this invention is to provide a kind of medium-sized pvc polymerizer, its volume and length-to-diameter ratio are suitable, reasonable in design, and heat-transfer effect is good, and sticking wall can continuous production, unit volume output height.
Another object of the present invention provides a kind of method that adopts above-mentioned polymeric kettle to carry out suspension polymerization vinylchlorid.
The present invention is achieved in that a kind of medium-sized polymeric kettle that is used for Production of PVC, comprises kettle, transmission mechanism, agitator, cooling jacket, and wherein: the kettle length-to-diameter ratio is 1.6-1.95, volume 40-60m
3Nominal diameter 2.5-4 rice, the high 4.5-7 rice of the direct tube section of still; Select transmission mechanism to adopt the top-extending type transmission mechanism, be made up of electric motor, step-down gear, shaft coupling and stir shaft, stir shaft is associated with the bottom supporting device; Agitator adopts two-layer three leaf swept-back stirring rakes, is installed on the stir shaft; The outer direct tube section of still is provided with the spirrillum semicanal, and still also is provided with spray valve outward, and still has the parts such as quick opening manhole of safety valve and band interlocking gear outward; Select novel PVC polymerization still release agent for use, rotary spray is coated with still, and the still situation is seen surplus moving 400, and sticking still situation is very light, but the unclear still of continuous operation 200 stills.Polyreaction adopts the control of DCS system, the total heat conduction area 70-85m of still
2, design pressure 1.5MPa in the still.The global design of still is carbon steel one stainless steel clad plate, and the still inwall adopts the electropolishing technology, and surface roughness Ra=0.1-0.2 μ m is equivalent to ceramic slickness.
Chloroethylene polymerization reactor of the present invention adopts three leaf swept-back agitators, diameter of propeller blade wherein and α, β angle are the significant dimensions of control fluid flow direction, directly influence mixing effect, among the present invention, the α angle is controlled at the 15-20 degree, and the γ angle is controlled at the 30-50 degree; When adopting two-layer three leaf swept-back agitators, the wording depth of every layer of agitator be the still internal diameter 1.2-1.5 doubly, diameter of propeller blade and kettle diameter ratio are 0.4, blade becomes greatly from inside to outside gradually; Adopt this structure, can reach full still volume Circulation.The rotating speed of mixing device is 80-150rpm, end of blade linear velocity 10m/s, and the highest end of blade linear velocity can reach 15m/s.
The present invention also adds inner cool tube and carries out conducting heat in the still from still top, remedying the deficiency of chuck heat transfer area, and heat-transfer effect is better, and the wall thickness of general inner cool tube is thinner, its hot COEFFICIENT K=930-1163W/ (m
2.K), the heat transfer area of inner cool tube is 30% of a chuck heat transfer area, but conducts 40% of polymerization reaction heat, and the heat transfer efficiency that inner cool tube is described is than chuck height.Inner cool tube adds from the still top, and maintenance, the cleaning of being convenient to inner cool tube are extracted out conveniently, and inner cool tube plays the effect of baffle plate in still in addition, cooperates agitator to make shearing action moderate, obtains cycling stream up and down, and reaction is evenly carried out; Be suitable for solid particulate below 10 orders, concentration is not more than 50%, the chloroethylene polymerization of viscosity below 100 centipoises.
Of the present invention another is characterised in that the supporting structure that is provided with stir shaft at the bottom of still, its radial and axial employing 0 RunddichtringO sealing, generally when chloroethylene polymerization, axle sleeve and bearing shell produce heat of friction when equipment operation, material enters easily and plastifies cladding because local superheating produces, with stir shaft " locking ", be difficult to clean, the present invention is provided with water structure and device in the still bottom, be furnished with waterflood pump and carry out continuous water filling, water is entered between axle sleeve and bearing shell, with material envelope position, overcome the seize problem, and played local refrigerative effect.
Polymeric kettle of the present invention, the preferred 1.75-1.85 of its length-to-diameter ratio, volume 40-50m
3Nominal diameter 2.5-3.5 rice; Most preferably the kettle length-to-diameter ratio is a 1.80-1.85 rice, volume 45m
3Nominal diameter 2.8-3.2 rice.
The present invention adopts the half-pipe jacket formula type of cooling, and still inwall and still inner member outer wall adopt electropolishing, and antiseized still effect, heat-transfer effect are good.The jacket structured water coolant that makes of semicanal spiral type rises along the semicanal spiral, can obtain big flow velocity (4m/s) with the little water yield, with the mode of many imports and multiple exit, has improved heat transfer coefficient better, and heat transfer coefficient can reach K=900W (m
2.K), be 1.4 times of spiral guide plate chuck, both improved heat transfer coefficient, increase the intensity of kettle again, lower cover adopts conventional jacket, and water-in is adorned a nozzle and is carried out jet.The temperature of polymeric kettle realizes DCS Controlling System automatization control in addition, in conjunction with the above-mentioned type of cooling, the polymeric kettle temperature variation can be controlled at ± 0.1-0.2 ℃ scope in, the heat transfer property of still is good, phenomenons such as overtemperature is uncontrollable can not occur.
The technology that adopts during polymerization is: add a certain amount of soft water, dispersion agent, auxiliary agent and initiator in the polymeric kettle in advance, stir, vacuumize pressure testing after, vinyl chloride monomer is sent in the polymeric kettle after under meter metering by the monomer transferpump.Vinylchlorid carries out suspension polymerization in polymeric kettle, generate polyvinyl chloride oar material.After polyreaction finishes, add terminator, stop polymerization, carry out unconverted monomer reclaimer operation in the still.After recovery finishes, with discharging pump polyvinyl chloride oar material is delivered in the groove that connects material, carried out precipitating and handle, the polyvinyl chloride oar material after the processing behind centrifugal, cyclone drying, send the wrapping machine packing, obtains finished product polychlorostyrene second resin.
According to the whipped form of this still, the heat-transfer effect and the production resin trade mark of still, adjust and optimize polymerization formula, unreacted vinyl chloride monomer is very easily separated in last handling process, polymerization oar material is through simple single kettle type stripping, obtain health level, medical grade PVC product, the product residue monomer content is less than 5ppm.The advantage of new prescription be polymerization exotherm evenly, product physical and mechanical properties and processing characteristics be good, add man-hour plasticization temperature than conventional with low 3 ℃ of trade mark polyvinyl chloride resin.All adopt No Poison on auxiliary agent is selected: polyethylene of dispersing agent alcohol, Vltra tears are the No Poison that can be used for food service industry; Initiator adopts innoxious solvent to replace benzene solvent; Other auxiliary agent such as terminator, defoamer, PH conditioning agent etc. all belong to No Poison.The trial production product in residual vinyl chloride content in 1～5ppm scope, 1,1-ethylene dichloride content＜150ppm, quality meets GB4803-94 " food product containers, wrapping material polyvinyl chloride (PVC) RESINS hygienic standard " requirement fully.
After polyreaction finished, unconverted monomer carried out reclaiming monomer from pressure, pressurization, the condensation of vacuum compression three phases from the still top through foam catcher, surge tank, water ring compressor, condenser, and the unconverted monomer rate of recovery is more than 95%; With pump oar material in the still is squeezed into the groove that connects material after MONOMER RECOVERY finishes,, need drip efficient gas phase stopper to system for making system's long-term safety smooth running.The whole recovery process is finished by the control of DCS microcomputer follow procedure.The main equipment of this technology has one of vacuum compressor, two of condensers.This recovery process characteristic is that recovery yield of monomer height, automatic control level height, running period are long.The successful Application of this operational path reclaims operational path for the same industry provides another unconverted monomer, and the colleague provides an energy-saving and cost-reducing new way for the PVC industry.
The resin oar material of gained makes the resin water capacity less than 24% through centrifuge dehydration.The dry air-flow that adopts of wet resin combines with cyclone drying.That this technology has is energy-saving and cost-reducing, simple to operate, be close to characteristics such as need not keep in repair.Whizzer inlet amount and cyclone dryer bed temperature interlocking, centrifugal drying adopts microcomputer control.The polyvinyl chloride resin screening is adopted and is revolved the sieve replacement trommel screen that shakes.
Vinyl chloride monomer and deionized water are carried with impeller pump by storage tank separately respectively, after the value given in advance of under meter metering on the pipeline, enter polymeric kettle, this technology saves the monomer and the deionized water scale tank of stainless steel, charging realizes that DCS controls automatically, operator and working strength of workers have been reduced, both saved initial cost, and increased the accuracy of metering again, technology level reaches advanced international level.
In the prior art, the fractionation tail gas treatment process is with-22 ℃ of brine refrigeration of tail gas warp, the superpressure emptying, and about 10% (V) of vent gas vinyl-chloride-containing, annual loss vinylchlorid is about 60 tons when producing ten thousand tons of PVC per year.Now adopt charcoal absorption, malleation desorption technique, the monomer that estimate to reclaim can be produced PVC200 ton/year (by 30,000 tons of PVC/), by PVC6500 per ton unit, annually increases by 1,300,000 yuan of incomes, and the while, the malleation desorption technique was than vacuum desorption technology safety and reliability.After adopting this technology, discharging can reduce by more than 200 ton of vinylchlorid to atmospheric pollution every year to sky.Not only protected environment but also increased economic benefit.
Above-mentioned polymerization technique prescription (weight percent) is as follows:
1) water 57-64%
2) vinylchlorid 41-35%
3) initiator 0.03-0.07%
4) dispersion agent 0.004-0.006%
5) PH conditioning agent 0.03-0.07%
6) thermo-stabilizer 0.03-0.07%
7) defoamer 0.01-0.03%
8) the terminator consumption is 0.03-0.07%
Wherein initiator can be superoxide (benzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate, the two ethylhexyls of peroxy dicarbonate etc.) or azo-compound (Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.).Dispersion agent can be compound for polyvinyl alcohol and Vltra tears, and thermo-stabilizer adopts organotin and 2, two pairs of butyl p-methyl phenols of 6-etc.
Polymerization unit of the present invention and method also can be used for the copolymerization of vinylchlorid and other vinyl monomer, add various vinyl monomers such as vinylformic acid, methacrylic acid and methylene-succinic acid as ethene, propylene and vinyl-acetic ester, unsaturated acid.
Two ethylhexyls (EHP) of the preferred peroxy dicarbonate of initiator of the present invention or Diisopropyl azodicarboxylate (ABIN), the pure and mild Vltra tears mixture of dispersion agent preferably polyethylene, the PH conditioning agent adopts sodium hydroxide or sodium bicarbonate composite sulfuration sodium or ammonium hydrogencarbonate, ammoniacal liquor etc., thermo-stabilizer adopts organotin and 2, two pairs of butyl p-methyl phenols of 6-also adopt modified silane defoamer and terminator dihydroxyphenyl propane in addition among the present invention.
Adopt the polyvinyl chloride product of technology of the present invention and device fabrication, (160 ℃ of number of impurity particles, screenings, apparent density, flake number, whiteness, 10min) wait key index to be far superior to " the universal polyvinyl chloride (PVC) RESINS national standard of suspension method " (GB/T5761-93), 1, indexs such as 1-ethylene dichloride content, vinylchlorid residual volume also meet " food product containers, wrapping material polyvinyl chloride (PVC) RESINS hygienic standard " (GB4803-94) fully, and the product top-quality product rate reaches 92.84%.
Polymeric kettle length-to-diameter ratio of the present invention is moderate, and unit volume output is big, can reach 222 tons/(cubic meter. year).The present invention adopts two-layer three leaves to plunder the formula stirring rake, and its stirring intensity shearing force and cycle index are more moderate, and product pellet is concentrated and even; The present invention adopts the top-extending type transmission, stable drive, and running period is long, and maintaining is convenient; Adopt the condensation of semicanal spiral type chuck, can obtain big flow velocity with the little water yield, so heat-transfer effect is good, adopt polymeric kettle of the present invention and technology polymerizing vinyl chloride, can obtain that particle form is good, even molecular weight distribution, higher, the black yellow point of oil absorbency and the few high-quality polyvinyl chloride product of brilliant point, and continuous production and still clearly.The successful Application of novel still of the present invention and corresponding technology is for China's PVC industry production has increased a new reator kind and novel process, with the development that promotes that China PVC produces.
The contrast accompanying drawing is described in detail the present invention in conjunction with the embodiments below:
Description of drawings:
Fig. 1 is the structural representation of the embodiment of the invention 1;
Fig. 2 is the sectional view of the bottom supporting device of embodiment 1;
Fig. 3 is the synoptic diagram of the three leaf swept-back stirring rakes of embodiment 1.
Embodiment 1
Referring to Fig. 1 and Fig. 2, the medium-sized polymeric kettle that is used for Production of PVC comprises kettle (1), transmission mechanism (2), agitator (3), cooling jacket (4).The transmission mechanism major part is positioned at outside the kettle, and agitator is positioned at kettle, cooling jacket parcel kettle.
Kettle (1) is provided with manhole (5) and supporting leg (6).Kettle (10) is chosen and is selected the making of carbon steel-stainless steel composition board, and its inwall carries out electropolishing.The length-to-diameter ratio of kettle in the present embodiment (1) is 1.9, and nominal volume is 45m
3, the diameter of still is 3m, actual useful volume is 46.6m
3
Transmission mechanism (2) adopts the top-extending type transmission mechanism, and promptly transmission mechanism is installed on the top cover of kettle (1), and passes top cover and connect with agitator (3).Transmission mechanism (2) by electric motor, subtract Quick culture machnie, shaft coupling, mechanically-sealing apparatus (7) and stir shaft (8) and form.Adopt the advantage of top-extending type transmission mechanism to be, can prolong sealing life, stable drive, running period is long, and maintaining is convenient, and manufacturing expense is relatively low.
Be associated with the bottom supporting device referring to Fig. 2 stir shaft (8).The bottom supporting device is made of axle sleeve (9), bearing shell (10) and watt frame (11).Watt frame (11) is associated with gland (12), takes by force to cover to have water filling port (13).Between watt frame (11) and the gland (12), and be provided with sealing-ring (14.15) between watt frame (11) and the kettle (1).The bottom supporting device has water injecting mechanism, and this water injecting mechanism is made of gap (not drawing among the figure) between axle sleeve (9) and the bearing shell (10) and water filling port (13).Water injecting mechanism can prevent that material from entering the gap of bearing shell and axle sleeve, avoids producing the plasticizing cladding with stir shaft (8) locking, and it finishes water filling in the kettle (1) when bearing shell and axle sleeve are played cooling effect.
Referring to Fig. 1, agitator (3) adopts two-layer three leaf swept-back stirring rakes.Its internal circulating load is big, and shearing action is moderate, makes the polymerization product particle distribution concentrate and even, and requirement and its stirring action height that can satisfy the polymerization heat transfer well are higher, and the wording depth of individual layer blade is 1.2D, can reach full still volume circulation requirement.The concrete structure of swept-back stirring rake as shown in Figure 3, wherein the α angle be 20 the degree, the γ angle be 30 the degree.
Referring to Fig. 1, cooling jacket (4) adopts semicanal spiral type chuck, and just water coolant rises along the semicanal spiral, can obtain big flow velocity (4m/s) with the little water yield.Semicanal spiral type chuck has a plurality of imports and a plurality of outlet, thereby has improved heat transfer coefficient better, and heat transfer coefficient can reach 900w/m
2.K.
In order further to improve the heat-transfer capability of polymeric kettle, also be provided with inner cool tube (16) in the present embodiment (1).4 inner cool tubes add from the top cover of kettle (1), are convenient to the inner cool tube maintenance, clean.
Present embodiment has been manufactured experimently out model machine and has been carried out production test.In the test, model machine safe operation 402 stills are produced 4424 tons of food grade polyvinyl chloride (PVC) RESINS.
Embodiments of the invention 2-5 sees Table 1, and table 1 has also been listed 7m of the prior art
3And 30m
3The parameter of polymeric kettle is seen comparative example 1-2, and comparative example 3-4 is that the polymeric kettle of prior art directly is enlarged into 45m
3The parameter of polymeric kettle, wherein comparative example 1-4 adopts paddle stirrer and chuck cooling.
Table 1
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Length-to-diameter ratio | ????1.6 | ????1.7 | ????1.8 | ???1.95 | ???2.08 | ??2.0 | ?2.08 | ?2.0 |
| Diameter M | ????3.5 | ????3.2 | ????3.0 | ????2.5 | ????2.6 | ??1.6 | ?2.8 | ?2.8 |
| Individual layer blade wording depth | ????1.2 | ????1.5 | ????1.3 | ????1.4 | ||||
| The α angle | ????18 | ????15 | ????16 | ????17 | ||||
| The γ angle | ????40 | ????45 | ????50 | ????35 | ||||
| Volume m 3 | ????45 | ????45 | ????45 | ????45 | ????30 | ????7 | ??45 | ??45 |
Embodiment 6
Adding-27T soft water, 1.1KG dispersion agent, 10KG auxiliary agent and 9.5KG initiator in advance in the polymeric kettle stir, vacuumize pressure testing after, the 16.5T vinyl chloride monomer is sent in the polymeric kettle after the under meter metering by the monomer transferpump.Vinylchlorid carries out suspension polymerization in polymeric kettle, after polyreaction finishes, add the 10KG terminator, stops polymerization, carries out unconverted monomer reclaimer operation in the still.After recovery finishes, with discharging pump polyvinyl chloride oar material is delivered in the groove that connects material, carried out precipitating and handle, the polyvinyl chloride oar material after the processing behind centrifugal, cyclone drying, send the wrapping machine packing, obtains finished product polychlorostyrene second resin.
Table 2-5 has listed and has adopted the foregoing description and the polymeric kettle of comparative example and quality product situation and the contrast of explained hereafter PVC.
Table 2.45m
3Polymeric kettle polyvinyl chloride (PVC) RESINS quality product situation.
| Viscosity number ml/g | Volatile matter % | Screenings % | Gritty particle several | Apparent density g/ml | Flake/400cm 2 | Vinylchlorid residual quantity (ppm) | 160 ℃ of 10min of ageing whiteness (%) | ||
| 0.25 mm | 0.063 ?mm | ||||||||
| Implement 1 example | ?124 | ????0.08 | ?0.4 | ?99.6 | ????10 | ?0.52 | ????3 | ????2 | ????81 |
| ?124 | ????0.11 | ?0.4 | ?99.6 | ????10 | ?0.52 | ????16 | ????2 | ????82 | |
| ?123 | ????0.24 | ?0.4 | ?99.6 | ????8 | ?0.51 | ????3 | ????1 | ????80 | |
| Implement 2 examples | ?122 | ????0.20 | ?0.4 | ?99.2 | ????10 | ?0.52 | ????6 | ????1 | ????80 |
| ?123 | ????0.25 | ?0.4 | ?99.6 | ????8 | ?0.51 | ????10 | ????1 | ????82 | |
| ?124 | ????0.24 | ?0.4 | ?99.6 | ????8 | ?0.51 | ????2 | ????1 | ????81 | |
| Implement 3 examples | ?123 | ????0.18 | ?0.4 | ?99.6 | ????16 | ?0.52 | ????15 | ????1 | ????80 |
| ?122 | ????0.19 | ?0.4 | ?99.6 | ????10 | ?0.53 | ????10 | ????1 | ????82 | |
| ?123 | ????0.14 | ?0.4 | ?99.6 | ????16 | ?0.52 | ????19 | ????2 | ????80 | |
| Implement 4 examples | ?125 | ????0.16 | ?0.4 | ?99.6 | ????6 | ?0.53 | ????11 | ????1 | ????82 |
| ?124 | ????0.14 | ?0.4 | ?99.6 | ????12 | ?0.51 | ????16 | ????3 | ????82 | |
| ?121 | ????0.18 | ?0.4 | ?99.6 | ????12 | ?0.53 | ????9 | ????1 | ????80 | |
| Implement 5 examples | ?124 | ????0.10 | ?0.4 | ?99.6 | ????10 | ?0.51 | ????5 | ????1 | ????83 |
| ?123 | ????0.10 | ?0.4 | ?99.2 | ????14 | ?0.52 | ????9 | ????1 | ????83 | |
| ?124 | ????0.13 | ?0.4 | ?99.6 | ????6 | ?0.53 | ????9 | ????1 | ????80 | |
| ?124 | ????0.13 | ?0.4 | ?99.6 | ????14 | ?0.52 | ????28 | ????2 | ????82 | |
Table 3.7m
3Polymeric kettle polyvinyl chloride (PVC) RESINS quality product situation
| Viscosity number ml/g | Volatile matter % | Screenings % | Gritty particle several | Apparent density g/ml | " flake " individual/400cm 2 | Vinylchlorid residual quantity (ppm) | 160 ℃ of 10min of ageing whiteness (%) | ||
| 0.25 ?mm | ?0.063 ?mm | ||||||||
| Comparative example 1 | ????123 | ????0.07 | ????52 | ????0.46 | ????108 | ????17 | ????72 | ||
| ????125 | ????0.16 | ????14 | ????0.46 | ????131 | ????14 | ????79 | |||
| ????123 | ????0.10 | ????48 | ????0.45 | ????45 | ????14 | ????71 | |||
| ????125 | ????0.08 | ????70 | ????0.44 | ????13 | ????211 | ????76 | |||
| ????122 | ????0.04 | ????22 | ????0.45 | ????18 | ????27 | ????72 | |||
| ????125 | ????0.03 | ????37 | ????0.43 | ????69 | ????187 | ????77 | |||
| ????123 | ????0.23 | ????16 | ????0.45 | ????412 | ????48 | ????77 | |||
| ????125 | ????0.18 | ????24 | ????0.43 | ????162 | ????10 | ????73 | |||
| Comparative example 3 | ????123 | ????0.26 | ????29 | ????0.44 | ????35 | ????503 | ????80 | ||
| ????122 | ????0.36 | ????84 | ????0.50 | ????70 | ????504 | ????73 | |||
| ????124 | ????0.18 | ????15 | ????0.50 | ????32 | ????462 | ????75 | |||
| ????124 | ????0.22 | ????32 | ????0.48 | ????27 | ????360 | ????76 | |||
| ????125 | ????0.04 | ????47 | ????0.47 | ????49 | ????70 | ????77 | |||
| ????119 | ????0.05 | ????62 | ????0.47 | ????516 | ????20 | ????79 | |||
| ????120 | ????0.12 | ????17 | ????0.47 | ????38 | ????17 | ????72 | |||
| ????119 | ????0.07 | ????37 | ????0.49 | ????70 | ????6 | ????76 | |||
| ????119 | ????0.06 | ????29 | ????0.47 | ????66 | ????16 | ????74 | |||
Table 4.30m
3Polymeric kettle polyvinyl chloride (PVC) RESINS quality product information slip
| Viscosity number ml/g | Volatile matter % | Screenings % | Gritty particle several | Apparent density g/ml | " flake " individual/400cm 2 | Vinylchlorid residual quantity (ppm) | 160 ℃ of 10min of ageing whiteness (%) | ||
| 0.25 ?mm | ?0.063 ??mm | ||||||||
| Comparative example 2 | ?120 | ?0.13 | ?0.2 | ?95.7 | ????25 | ?0.47 | ????10 | ????0.5 | |
| ?122 | ?0.16 | ?0.2 | ?96.6 | ????18 | ?0.46 | ????12 | ????2 | ||
| ?123 | ?0.15 | ?0.2 | ?95.6 | ????42 | ?0.47 | ????21 | ????0.9 | ||
| ?122 | ?0.11 | ?0.2 | ?98.3 | ????22 | ?0.47 | ????16 | ????0.1 | ||
| ?123 | ?0.11 | ?0.2 | ?97.6 | ????18 | ?0.47 | ????13 | ????0.9 | ||
| ?120 | ?0.11 | ?0.2 | ?98.2 | ????16 | ?0.49 | ????21 | ????3 | ||
| ?126 | ?0.08 | ?0.2 | ?99.8 | ????50 | ?0.46 | ????13 | ????2 | ||
| ?122 | ?0.12 | ?0.2 | ?99.4 | ????42 | ?0.46 | ????27 | ????2.6 | ||
| Comparative example 4 | ?122 | ?0.14 | ?0.2 | ?99.5 | ????18 | ?0.46 | ????14 | ????1.2 | |
| ?123 | ?0.22 | ?0.2 | ?97.8 | ????20 | ?0.49 | ????13 | ????28 | ||
| ?122 | ?0.10 | ?0.2 | ?97.6 | ????12 | ?0.46 | ????19 | ????2.2 | ||
| ?124 | ?0.11 | ?0.2 | ?99.3 | ????35 | ?0.48 | ????13 | ????2 | ||
| ?122 | ?0.20 | ?0.2 | ?98.3 | ????35 | ?0.49 | ????10 | ????3.5 | ||
| ?122 | ?0.14 | ?0.2 | ?95.2 | ????10 | ?0.47 | ????10 | ????2 | ||
| ?123 | ?0.15 | ?0.2 | ?97.2 | ????18 | ?0.48 | ????14 | ????3.0 | ||
| ?122 | ?0.12 | ?0.2 | ?99.3 | ????17 | ?0.48 | ????15 | ????2.5 | ||
| ?124 | ?0.16 | ?0.2 | ?95.7 | ????10 | ?0.49 | ????10 | ????2 | ||
From table 2--4 as can be seen, 45m
3The PVC product that still is produced all is better than 7m at aspects such as number of impurity particles, apparent density, " flake ", vinylchlorid residual quantity, ageing whiteness and screeningss
3And 30m
3Still.Leading indicator relatively sees Table 5.
Table 5.
Because 45m
3Still adopts the electropolishing technology, inner form the still release agent of smooth surface, employing and be coated with that still liquid is superior in quality, prescription rationally, the kettle pasting matter of generation is obviously reduced, so " flake " in the product reduces greatly; The smooth surface of polishing technology formation can also prevent the pollution of iron ion to material in addition, the continuous water filling device that the lower shaft envelope is provided with, avoided entering and forming the plasticizing cladding, thereby number of impurity particles obviously reduces in the product at polymerization process axis and axle sleeve frictional heat resin; The mode of " big flow, the low temperature difference " is adopted in this still heat exchange, makes the reaction process temperature fluctuation minimum, and prescription is reasonable in addition, auxiliary agent is good, and resin particle is evenly distributed, and ageing whiteness improves; Because MONOMER RECOVERY adopts advanced technology, makes the contained vinyl chloride monomer of resin reach the requirement of health level.
Table 6 has been listed the present China and the world main polymeric kettle unit volume production capacity situation.
| Country | Company | The still volume, m3 | The unit volume production capacity, t/m3 |
| China | The Jinxi machine | ????33 | ????152 |
| China | Qingdao Hai Jing | ????45 | ????222 |
| The U.S. | The Gu Te Ritchie | ????70 | ????284 |
| Japan | SHIN-ETSU HANTOTAI | ????127 | ????197 |
| Germany | Xu Ersi | ????200 | ????250 |
As can be seen from Table 6,45m of the present invention
3Polymeric kettle unit volume production capacity maintains the leading position.
Claims (20)
1. the method for suspension polymerization vinylchlorid adopts the medium-sized polymeric kettle that comprises kettle, transmission mechanism, agitator, refrigerating unit, it is characterized in that medium-sized polymeric kettle structure is:
1). the kettle length-to-diameter ratio is 1.6-1.95, nominal diameter 2.5-4 rice, volume 40-60m
3
2). transmission mechanism adopts the top-extending type transmission mechanism, is made up of electric motor, step-down gear, shaft coupling, tightness system and stir shaft, and stir shaft is associated with the bottom supporting device;
3). agitator adopts three leaf swept-back stirring rakes, is installed on the stir shaft;
4). cooling jacket adopts semicanal spiral type chuck.
The technology that polymerization is adopted is:
1). add a certain amount of soft water, dispersion agent, auxiliary agent and initiator in the polymeric kettle in advance, stir, vacuumize pressure testing;
2). vinyl chloride monomer is sent into after the under meter metering in the inherent polymeric kettle of polymeric kettle by the monomer transferpump and is carried out suspension polymerization;
3) after polyreaction finishes, add terminator;
4) reclaim unconverted monomer in the still;
5) discharging pump is delivered in the groove that connects material precipitating with polyvinyl chloride oar material and is handled, and the polyvinyl chloride oar material after the processing behind centrifugal, cyclone drying, obtains finished product polychlorostyrene second resin.
2. polymeric kettle according to claim 1 is characterized in that: described bottom supporting device is made of axle sleeve, bearing shell, watt frame and water injecting mechanism.
3. polymeric kettle according to claim 1 is characterized in that the bottom supporting device, and water injecting mechanism is made of gap between axle sleeve and the bearing shell and water filling port.
4. polymeric kettle according to claim 1 is characterized in that: be provided with inner cool tube in the kettle.
5. polymeric kettle according to claim 1 is characterized in that: semicanal spiral type chuck has a plurality of imports and a plurality of outlet.
6. polymeric kettle according to claim 1 is characterized in that preferred kettle length-to-diameter ratio is 1.75-1.85, volume 40-50m
3Nominal diameter 2.5-3.5 rice.
7. polymeric kettle according to claim 6 is characterized in that the preferred 1.80-1.85 of length-to-diameter ratio, volume 45m
3Nominal diameter 2.8-3.2 rice.
8. polymeric kettle according to claim 1 is characterized in that three leaf swept-back stirring rakes for double-deck, and the wording depth of every layer of agitator is 1.2-1.5 a times of still internal diameter.
9. polymeric kettle according to claim 7, the α angle that it is characterized in that two-layer three leaf swept-back stirring rakes is the 15-20 degree, the γ angle is the 30-50 degree.
10. polymeric kettle according to claim 8 is characterized in that two-layer three leaf swept-back stirring rake diameter of propeller blade are 0.43 with kettle diameter ratio.
11. a medium-sized polymeric kettle that is used for Production of PVC comprises kettle, transmission mechanism, agitator, refrigerating unit, it is characterized in that:
1). the kettle length-to-diameter ratio is 1.6-1.95, nominal diameter 2.5-4 rice, volume 40-60m
3
2). transmission mechanism adopts the top-extending type transmission mechanism, is made up of electric motor, step-down gear, shaft coupling, tightness system and stir shaft, and stir shaft is associated with the bottom supporting device;
3). agitator adopts three leaf swept-back stirring rakes, is installed on the stir shaft;
4). cooling jacket adopts semicanal spiral type chuck.
12. polymeric kettle according to claim 11 is characterized in that: described bottom supporting device has water injecting mechanism.
13. polymeric kettle according to claim 12, it is characterized in that the bottom supporting device by axle sleeve, bearing shell, watt be configured to, water injecting mechanism is made of gap between axle sleeve and the bearing shell and water filling port.
14. polymeric kettle according to claim 11 is characterized in that: be provided with inner cool tube in the kettle.
15. polymeric kettle according to claim 11 is characterized in that: semicanal spiral type chuck has a plurality of imports and a plurality of outlet.
16. polymeric kettle according to claim 11 is characterized in that the preferred 1.75-1.85 of kettle length-to-diameter ratio, volume 40-50m
3Nominal diameter 2.5-3.5 rice.
17. polymeric kettle according to claim 16 is characterized in that most preferably 1.80-1.85 of length-to-diameter ratio, volume 45m
3Nominal diameter 2.8-3.2 rice.
18. polymeric kettle according to claim 1 is characterized in that three leaf swept-back stirring rakes for double-deck, the wording depth of every layer of agitator is 1.2-1.5 a times of still internal diameter.
19. polymeric kettle according to claim 7, the α angle that it is characterized in that two-layer three leaf swept-back stirring rakes is the 15-20 degree, and the γ angle is the 30-50 degree.
20. polymeric kettle according to claim 8 is characterized in that two-layer three leaf swept-back stirring rake diameter of propeller blade are 0.43 with kettle diameter ratio.
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|---|---|---|---|
| CN 00103984 CN1124295C (en) | 2000-03-21 | 2000-03-21 | Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00103984 CN1124295C (en) | 2000-03-21 | 2000-03-21 | Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process |
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| Publication Number | Publication Date |
|---|---|
| CN1314421A true CN1314421A (en) | 2001-09-26 |
| CN1124295C CN1124295C (en) | 2003-10-15 |
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|---|---|---|---|
| CN 00103984 Expired - Lifetime CN1124295C (en) | 2000-03-21 | 2000-03-21 | Medium size polymerizing still for suspension polymerizing vinyl chloride and relevant polymerization process |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341905C (en) * | 2005-10-25 | 2007-10-10 | 上海氯碱化工股份有限公司 | Polymerization reactor for producing suspension type polyvinyl-chloride |
| CN100347200C (en) * | 2005-01-11 | 2007-11-07 | 锦化化工（集团）有限责任公司 | Method for reusing polyvinyl chloride pulp centrifuged mother liquor |
| CN100558765C (en) * | 2005-02-05 | 2009-11-11 | 锦化化工（集团）有限责任公司 | Adopt 70.5m 3Polymeric kettle is produced the method for polyvinyl chloride |
| CN101735373B (en) * | 2009-12-18 | 2011-11-09 | 昊华宇航化工有限责任公司 | New process for SG3 type PVC (polyvinyl chloride) resin production |
| CN102247792A (en) * | 2011-04-30 | 2011-11-23 | 甘肃银光聚银化工有限公司 | Novel polyphase stirred reactor |
| CN103170297A (en) * | 2013-03-19 | 2013-06-26 | 葫芦岛华远化工机械装备有限公司 | Horizontal type dispersion polymerization kettle for producing polyvinylidene fluoride |
| CN104677001A (en) * | 2015-02-11 | 2015-06-03 | 佛山市特赛化工设备有限公司 | Vacuum cooling warehousing and vacuum delivering system for high-viscosity materials |
| CN107869929A (en) * | 2017-11-21 | 2018-04-03 | 鄂尔多斯市君正能源化工有限公司 | A kind of reactor inner cool tube fixing device and the reactor containing it |
| CN112805085A (en) * | 2018-10-15 | 2021-05-14 | 韩华思路信(株) | Batch reactor |
| CN114390945A (en) * | 2019-09-10 | 2022-04-22 | 韩华思路信株式会社 | Batch stirrer for vinyl chloride resin suspension polymerization and batch suspension polymerization reactor using same |
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2000
- 2000-03-21 CN CN 00103984 patent/CN1124295C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347200C (en) * | 2005-01-11 | 2007-11-07 | 锦化化工（集团）有限责任公司 | Method for reusing polyvinyl chloride pulp centrifuged mother liquor |
| CN100558765C (en) * | 2005-02-05 | 2009-11-11 | 锦化化工（集团）有限责任公司 | Adopt 70.5m 3Polymeric kettle is produced the method for polyvinyl chloride |
| CN100341905C (en) * | 2005-10-25 | 2007-10-10 | 上海氯碱化工股份有限公司 | Polymerization reactor for producing suspension type polyvinyl-chloride |
| CN101735373B (en) * | 2009-12-18 | 2011-11-09 | 昊华宇航化工有限责任公司 | New process for SG3 type PVC (polyvinyl chloride) resin production |
| CN102247792A (en) * | 2011-04-30 | 2011-11-23 | 甘肃银光聚银化工有限公司 | Novel polyphase stirred reactor |
| CN103170297A (en) * | 2013-03-19 | 2013-06-26 | 葫芦岛华远化工机械装备有限公司 | Horizontal type dispersion polymerization kettle for producing polyvinylidene fluoride |
| CN104677001A (en) * | 2015-02-11 | 2015-06-03 | 佛山市特赛化工设备有限公司 | Vacuum cooling warehousing and vacuum delivering system for high-viscosity materials |
| CN107869929A (en) * | 2017-11-21 | 2018-04-03 | 鄂尔多斯市君正能源化工有限公司 | A kind of reactor inner cool tube fixing device and the reactor containing it |
| CN107869929B (en) * | 2017-11-21 | 2024-05-03 | 鄂尔多斯市君正能源化工有限公司 | Cold pipe fixing device and contain its reation kettle in reation kettle |
| CN112805085A (en) * | 2018-10-15 | 2021-05-14 | 韩华思路信(株) | Batch reactor |
| CN114390945A (en) * | 2019-09-10 | 2022-04-22 | 韩华思路信株式会社 | Batch stirrer for vinyl chloride resin suspension polymerization and batch suspension polymerization reactor using same |
| CN114390945B (en) * | 2019-09-10 | 2023-12-12 | 韩华思路信株式会社 | Batch stirrer for suspension polymerization of vinyl chloride resin and batch suspension polymerization reactor using the same |
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