CN102161718A - Method and device for continuously producing chlorinated polyvinyl chloride by low-temperature plasma circulating bed - Google Patents
Method and device for continuously producing chlorinated polyvinyl chloride by low-temperature plasma circulating bed Download PDFInfo
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- CN102161718A CN102161718A CN 201110061421 CN201110061421A CN102161718A CN 102161718 A CN102161718 A CN 102161718A CN 201110061421 CN201110061421 CN 201110061421 CN 201110061421 A CN201110061421 A CN 201110061421A CN 102161718 A CN102161718 A CN 102161718A
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- 239000004801 Chlorinated PVC Substances 0.000 title claims abstract description 59
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 80
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 72
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 71
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010924 continuous production Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 238000007872 degassing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 82
- 238000005660 chlorination reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000012530 fluid Substances 0.000 description 7
- 238000005243 fluidization Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009840 oxygen flask method Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a method and device for continuously producing chlorinated polyvinyl chloride by a low-temperature plasma circulating bed, relating to a production technology and equipment for macromoleclar polymer chlorinated polyvinyl chloride. The device comprises a chlorinated polyvinyl chloride particle storage bin, a chlorinated polyvinyl chloride storage bin, two parallel fluidized bed reactors, two parallel riser reactors, a downer, a tail gas purifier and two circulating fans which are respectively used for transporting riser conveying gas and transporting raw material gas. In the device, the low-temperature plasma is utilized to simultaneously activate chlorine and PVC (poly vinyl chloride) raw material particles to quickly chloridize PVC in the circulating fluidized bed; and meanwhile, two groups of fluidized bed reactors are adopted for operation in turn to realize continuous production. Thus, the problems of low production efficiency and the like brought by that the reactor stops and unloads can be avoided, the phenomenon that fans, tail gas processors and the like are restarted after stopping can be eliminated, energy consumption is saved, and the service life of equipment is prolonged.
Description
Technical field
The present invention relates to method and device that a kind of gas-solid is combined to chlorinated polyvinyl chloride (CPVC), be particularly related to a kind of method that adopts low-temperature plasma circulating fluidize bed reactor continuous production CPVC, belong to the synthesis technique and the equipment of a kind of macromolecular material in the chlorine industry.
Background technology:
Chlorinated polyvinyl chloride (CPVC) is a kind of novel high-performance plastics.It is to be raw material with polyvinyl chloride (PVC), makes by reaction chlorating means, and cl content rises to 60%～70% by 56.8% of PVC, reaches as high as 73.2% in theory, and general CPVC cl content is 61%～68%.Because the raising of polarity constituent content, CPVC shows a series of characteristics that are better than PVC greatly: vicat softening temperature reaches 90～125 ℃, after treatment, 110 ℃ of maximum operation (service) temperatures, 95 ℃ of life-time service temperature have better weather resistance, erosion resistance and ageing resistance.
CPVC has high cost performance, and extensive market prospects and very big using value are arranged; Can be widely used in the cold and hot water pipeline, fields such as material of construction.Simultaneously, development CPVC project can consume the superfluous chlorine in the chlorine industry, and is significant.Existing C PVC production technique mainly comprises solution method, water phase suspension, gas-solid phase chlorination process, liquid chlorine chlorination process.Water phase suspension is the production method that present each major company generally takes, because still there is the product separation complexity in water method CPVC synthesis technique, the waste reaction solution discharging is serious, contaminate environment, shortcomings such as production environment is more abominable, gas-solid phase chlorination process is owing to its clean and effective, and the characteristics that are easy to control are subjected to extensive concern.
Low-temperature plasma CPVC synthetic technology is new, a promising CPVC route of synthesis, the method (CN1749285A) of a kind of chloridizing high molecule polymer by low temperature plasma of the Meng Yuedong of Hefei Inst. of Plasma Physics, Chinese Academy of Sciences and Xiong Xinyang invention, its characteristics are to finish the chlorination process of high molecular polymer in same plasma reactor, but the highest cl content of CPVC that obtains is 64.5%.In the article of the piece of writing " the low-temperature plasma vapor phase process prepares chlorinated polyvinyl chloride " by name that Xiong Xinyang equals to deliver in 2006, in a traditional fluidized-bed, realized the PVC chlorination, yet its chlorination result only can reach 59.4%.Tsing-Hua University's chemical industry is " the spouted bed bioreactor and the method thereof of low-temperature plasma synthesizing chlorinated polyvinyl chloride " CN200880015695.3 and " method of preparing chlorinated polyvinyl chloride by low-temperature plasma circulating fluidize bed and device " CN200910092928.6 of invention such as the breadboard Cheng Yi of reaction engineering, the reactor types that successful first employing is different, realized that as initiator the CPVC gas-solid is combined to low-temperature plasma, obtain cl content and be higher than 65%, reach as high as 69% CPVC product, but can not realize continuous production." a kind of devices and methods therefor of preparing chlorinated polyvinyl chloride by gas-solid phase method " of invention such as the Wang Jianying of Hebei University of Science and Technology, adopt circulating fluid bed reactor, with the UV-light is that initiator has been realized CPVC production, but does not realize continuous production, does not also relate to low-temperature plasma.
Summary of the invention
The objective of the invention is to propose concise and to the point flow process of method and the device of a kind of continuously synthetic CPVC, comprise the preheating of PVC raw material, can realize CPVC quantity-produced circulating fluid bed reactor, the degassing of CPVC product is handled, and workshop section such as tail gas clean-up absorption.Aspect reactor design, adopt two groups of fluidized-bed reactors and two groups of shared one group of descending-bed reactors of riser reactor, the mode of wheel flow operation realizes CPVC gas-solid phase continuous production.The production efficiency that adopts this method can avoid causing owing to reactor shutdowns descends problems such as wastage of material.
For achieving the above object, technical scheme provided by the invention is as follows:
The invention provides a kind of device of low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride, this device comprises that one is used for storing and preliminary preheating material PVC particulate polyvinyl chloride particles feed bin; Two the first class bed bioreactors that are arranged in juxtaposition and second fluidized-bed reactor, two fluidized reactors are connected with the polyvinyl chloride particles feed bin by carrier pipe respectively; A descending-bed reactor, this descending-bed reactor are connected with the bottom of two fluidized-bed reactors by the pipeline that has control valve respectively, in this descending-bed reactor inside the low-temperature plasma generating unit are housed; Two first riser reactors that are arranged in juxtaposition and second riser reactor, the bottom of two riser reactors is connected with the bottom of descending-bed reactor by the pipeline that has control valve respectively, the top of two riser reactors is connected by the top of gas-solid separator with two fluidized-bed reactors respectively, in each riser reactor inside the low-temperature plasma generating unit is housed all; Article two, be used for removing the hydrogenchloride of reaction end gas, make the pipeline of the chlorine recycle in the system, this pipeline comprises an exhaust gas cleaner and two recirculation blowers that are respectively applied for conveying riser tube conveying gas and unstripped gas; And one be used to store product, and possess the chlorinated polyvinyl chloride feed bin of degassing function.
Be provided with stirring rake in described two fluidized-bed reactors that are arranged in juxtaposition, to guarantee the PVC particle under the effect of stirring and unstripped gas, active fluidization in reactor is realized gas-solid phase uniform contact.Be provided with heating jacket 8 in individual fluidized-bed reactor outside, its fluidized-bed reactor
The low-temperature plasma that is adopted is dielectric barrier discharge plasma, radio-frequency plasma or microwave plasma.Discharge mode comprises two kinds of intermittent discharge and continuous discharges.
The invention allows for the method for the low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride that a kind of employing installs according to claim 1, this method may further comprise the steps:
The PVC particle at first joins one of them fluidized-bed reactor be preheated to 60～80 ℃ in the polyvinyl chloride particles feed bin after; Feed unstripped gas in the fluidized-bed reactor after adding the PVC particle, the PVC particle is reacted with unstripped gas in fluidized-bed reactor, unstripped gas is the gas mixture of chlorine or chlorine and rare gas element, temperature of reaction is 60～140 ℃, the residence time is 5～30min, and the operation absolute pressure is respectively 0.1atm～1.5atm; The service temperature of PVC particle in riser reactor and descending-bed reactor is 20～140 ℃, and the residence time is 0.1s～2min, and the operation absolute pressure is 0.1atm～1atm; In riser reactor and descending-bed reactor, the power density of low-temperature plasma is 0.1～10W/cm
3Reacted PVC particle flows out from the bottom of first class bed bioreactor, enter the bottom of riser reactor through descending-bed reactor, under the effect of riser tube conveying gas, enter the gas-solid separator on fluidized-bed reactor top, get back in the fluidized-bed reactor, the circulation of realization particle, it is the gas mixture of chlorine, rare gas element or chlorine and rare gas element that riser tube is carried gas. Tail gas after unstripped gas and PVC particle react and riser tube carry gas and the tail gas of PVC particle after gas solid separation to flow out from the fluidized-bed reactor top, enter exhaust gas cleaner except that behind the de-chlorine hydride, enter fluidized-bed reactor and riser reactor recycle through recirculation blower; After the reaction times reached 30min～4h, the chlorinated polyvinyl chloride product in the fluidized-bed reactor entered the chlorinated polyvinyl chloride feed bin, at 60～80 ℃ of 1～2h that outgas down; Close first descending control valve, the first riser tube control valve, first riser tube conveying gas control valve, the first unstripped gas control valve simultaneously, open second descending control valve, the second riser tube control valve, second riser tube conveying gas control valve, the second unstripped gas control valve; In another fluidized-bed reactor, repeat above-mentioned steps.By this operation, realize the continuous production of CPVC.
The present invention has following advantage than existing technology:
Problems such as 1. this invention can realize the continuous production of chlorinated polyvinyl chloride, has avoided owing to reactor shutdowns, and the production efficiency that discharging brought reduces, and reactor is perishable;
2. the operating method that adopts this invention and proposed, compare with periodical operation, can only change the gas and the heat flow direction by the mode that changes control valve, and do not change the general input of gas and heat, can avoid making blower fan like this, parkings such as exhaust gas processing device are restarted, and have saved energy consumption greatly, have prolonged equipment life.
Description of drawings
Fig. 1 is the structural principle synoptic diagram of continuous synthetic circulating fluid bed reactor of low-temperature plasma chlorinated polyvinyl chloride provided by the invention and simple process flow.
Among the figure: the 1-gas-cleaning installation; 2A-first recirculation blower; 2B-second recirculation blower; 3-low-temperature plasma generating unit; 4A-first riser reactor; 4B-second riser reactor; The 5-motor; The 6-gas-solid separator; 7A-first class bed bioreactor; 7B-second fluidized-bed reactor; The 8-heating jacket; The 9-stirring rake; The 10-gas distribution grid; 11-polyvinyl chloride particles feed bin; 12-chlorinated polyvinyl chloride feed bin; The 13-descending-bed reactor; The 14A-first riser tube control valve; The 14B-second riser tube control valve; First descending control valve of 15A-; Second descending control valve of 15B-; The 16A-first unstripped gas control valve; The 16B-second unstripped gas control valve; 17A-first riser tube is carried gas control valve; 17B-second riser tube is carried gas control valve; The A-unstripped gas; The B-tonifying Qi; The C-riser tube is carried gas
Embodiment
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing.This device comprises that one is used for storing and preliminary preheating material PVC particulate polyvinyl chloride particles feed bin 11, two the first class bed bioreactor 7A that are arranged in juxtaposition and the second fluidized-bed reactor 7B, two reactors are connected with polyvinyl chloride particles feed bin 11 by carrier pipe respectively; A descending-bed reactor 13, this descending-bed reactor 13 is connected with the bottom of two fluidized-bed reactors by the pipeline that has first descending control valve 15A and second descending control valve 15B respectively, in these descending-bed reactor 13 inside low-temperature plasma generating unit 3 is housed; First riser reactor 4A that two are arranged in juxtaposition and the bottom of the second riser reactor 4B are connected with the bottom of descending-bed reactor by first descending control valve 14A and second descending control valve 14B respectively; The top of two riser reactors is connected by the top of gas-solid separator 6 with two fluidized-bed reactors respectively; In each riser reactor inside low-temperature plasma generating unit 3 is housed all; Article two, be used for removing the hydrogenchloride of reaction end gas, make the pipeline of the chlorine recycle in the system, this pipeline comprises an exhaust gas cleaner 1 and two the first recirculation blower 2A and second recirculation blower 2B that are used for carrying respectively riser tube conveying gas and unstripped gas; And one be used to store product, and possess the chlorinated polyvinyl chloride feed bin 12 of degassing function.
Described two fluidized-bed reactor inside that are arranged in juxtaposition are provided with stirring rake 9, and to guarantee the PVC particle under the effect of stirring and unstripped gas, active fluidization in reactor is realized gas-solid phase uniform contact.Lower bottom part in fluidized-bed reactor is provided with gas distribution grid 10, and its outside is provided with heating jacket 8.
The low-temperature plasma that is adopted is dielectric barrier discharge plasma, radio-frequency plasma or microwave plasma.Discharge mode comprises two kinds of intermittent discharge and continuous discharges.
Operate to example earlier with the first class bed bioreactor below, working process of the present utility model be described as follows:
The PVC particle feeds chlorine and chlorine and rare gas element in the polyvinyl chloride particles feed bin gas mixture comes preheating, preheating temperature is 60～80 ℃, add in the feed bin and stir to guarantee the particle good distribution, feed bin is operated under normal pressure, after reaching preheating temperature, the PVC particle joins among the first class bed bioreactor 7A at first fast by carrier pipe, add-on is decided according to volume of industrial production, is generally between 100Kg～1t.
Meanwhile, feed unstripped gas A in the first class bed bioreactor after adding the PVC particle, open stirring rake 9 simultaneously, rotating speed is about 30～240rpm.Under the promotion of the disturbance of stirring rake and unstripped gas, the PVC particle suspends in fluidized-bed reactor, realizes gas-solid well contact mutually.This moment, chlorination reaction was slowly carried out owing to do not add initiator.Add inlet by heated oil and add heated oil, be incubated by 8 pairs of beds of heating jacket, so that the PVC particle carries out chlorination reaction near maintaining softening temperature.Unstripped gas is the gas mixture of chlorine or chlorine and rare gas element, and the chlorine volume fraction is 30% to 100% in the unstripped gas.The operation absolute pressure is 0.1atm～1.5atm among the first class bed bioreactor 7A.According to the increase gradually of PVC cl content, service temperature also raises gradually, and the integrated operation temperature range is 60～140 ℃.
Open the first descending control valve 15A and the first riser tube control valve 14A, the PVC particle is fallen by action of gravity, flow out from the bottom of first class bed bioreactor, enter the bottom of the first riser reactor 4A through descending-bed reactor 13, under the effect of riser tube conveying gas B, enter the gas-solid separator 6 on first class bed bioreactor top, get back in the first class bed bioreactor, the circulation of realization particle, it is chlorine that riser tube is carried gas, the gas mixture of rare gas element or chlorine and rare gas element, the chlorine volume fraction is 0～50%, open low-temperature plasma electrical source simultaneously, produce plasma area in first riser reactor and descending-bed reactor, the power density of low-temperature plasma is 0.1～10W/cm
3Adopt the descending bed of regulation and control control valve 15A, riser tube control valve 14A aperture, and the method for riser tube delivery air amount, control grain flux in first riser reactor, making the residence time of particle in first riser reactor is 0.1s～2min, and the residence time in the first class bed bioreactor is 5～30min, and the operation absolute pressure is 0.1atm～1atm, riser tube need not heat, and service temperature is 20～140 ℃.
Tail gas after unstripped gas and PVC particle react and riser tube carry gas and the tail gas of PVC particle after gas solid separation to flow out from the fluidized-bed reactor top, enter exhaust gas cleaner 1 except that behind the de-chlorine hydride, through the recirculation blower pressurization, B mixes mutually with tonifying Qi, and tonifying Qi B is pure chlorine.Enter the first class bed bioreactor and the first riser reactor recycle.
When particle circulates in the first class bed bioreactor and first riser reactor, according to given processing condition, after total reaction time reaches 30min～4h, close first descending control valve 15A, the first riser tube control valve 14A, first riser tube conveying gas control valve 17A and the first unstripped gas control valve 16A simultaneously, open second descending control valve 15B, the second riser tube control valve 14B, second riser tube conveying gas control valve 17B and the second unstripped gas control valve 16B; In the second fluidized-bed reactor 7B and the second riser reactor 4B, repeat PVC charging mentioned above, stirring and ciculation fluidized, steps such as reaction repeat this operation, realize the continuous production of CPVC.Chlorinated polyvinyl chloride product input chlorinated polyvinyl chloride feed bin in the first class bed bioreactor, bubbling air or rare gas element in the feed bin obtain product behind the degassing 1～2h down at 60～80 ℃.
Median size is the PVC particle of 150 μ m, and by the charging bole first fluidized bed of packing into, charge amount is 1 ton.The ON cycle blower fan is with Cl
2Concentration is 30% Cl
2/ Ar mixed gas feeds fluidized-bed, and the unlatching stirring makes PVC particle active fluidization.Add heated oil in chuck, keeping the interior PVC particle temperature of fluidized-bed is 100 ℃.The control valve of opening between the first fluidized bed and low-temperature plasma descending-bed reactor makes the PVC particle enter the low-temperature plasma descending-bed reactor, and riser reactor, causes chlorination in the low-temperature plasma tagma.Riser tube and descending bed are operated under normal pressure, and temperature is 100 ℃, particle residence time 20s.The solid PVC particle is got back to the first fluidized bed through gas solid separation, finishes the primary particle circulation.The residence time of particle in fluidized-bed is 10min.The reaction end gas of gas after the separation and first fluidized bed output together enters gas-cleaning installation and purifies after recirculation blower is got back to circulating fluid bed reactor.
Particle is pressed said process, circulates in the first fluidized bed and reaction of low temperature plasma device.Meanwhile, carry out charging mentioned above, operations such as preheating particulate in second fluidized-bed.After the total reaction time of particle in the first fluidized bed and reaction of low temperature plasma device reaches 2h, PVC draws off reactor with products C, after the degassing, adopts oxygen flask combustion method (GB 9872-1988) to record in the CPVC feed bin, cl content 67.24% meets the CPVC production requirement.
Embodiment 2:
Median size is the PVC particle of 200 μ m, and by the charging bole first fluidized bed of packing into, charge amount is 1 ton.The ON cycle blower fan is with Cl
2Concentration is 30% Cl
2/ Ar mixed gas feeds fluidized-bed, and the unlatching stirring makes PVC particle active fluidization.Add heated oil in chuck, particle is warming up to constant gradually from 70 ℃, and keeping the interior PVC particle temperature of fluidized-bed is 100 ℃.The control valve of opening between the first fluidized bed and low-temperature plasma descending-bed reactor makes the PVC particle enter low-temperature plasma descending-bed reactor and riser reactor, causes chlorination in the low-temperature plasma tagma.Riser tube and descending bed are operated under normal pressure, and temperature is 20 ℃, particle residence time 2min.The solid PVC particle is got back to the first fluidized bed through gas solid separation, finishes the primary particle circulation.The residence time of particle in fluidized-bed is 8min.The reaction end gas of gas after the separation and first fluidized bed output together enters gas-cleaning installation and purifies after recirculation blower is got back to circulating fluid bed reactor.
Particle is pressed said process, circulates in the first fluidized bed and reaction of low temperature plasma device.Meanwhile, carry out charging mentioned above, operations such as preheating particulate in second fluidized-bed.After the total reaction time of particle in the first fluidized bed and reaction of low temperature plasma device reaches 2h, PVC draws off reactor with products C, after the degassing, adopts oxygen flask combustion method (GB9872-1988) to record in the CPVC feed bin, cl content 68.6% meets the CPVC production requirement.
Embodiment 3:
Median size is the PVC particle of 150 μ m, and by the charging bole first fluidized bed of packing into, charge amount is 1 ton.The ON cycle blower fan is with Cl
2Concentration is 30% Cl
2/ Ar mixed gas feeds fluidized-bed, and the unlatching stirring makes PVC particle active fluidization.In chuck, add heated oil, heat up gradually, make that the PVC particle is the highest in the fluidized-bed is warming up to 140 ℃.The control valve of opening between the first fluidized bed and low-temperature plasma descending-bed reactor makes the PVC particle enter the low-temperature plasma descending-bed reactor, and riser reactor, causes chlorination in the low-temperature plasma tagma.Riser tube and descending bed are operated under normal pressure, and temperature is 140 ℃, particle residence time 10s.The solid PVC particle is got back to the first fluidized bed through gas solid separation, finishes the primary particle circulation.The residence time of particle in fluidized-bed is 10min.The reaction end gas of gas after the separation and first fluidized bed output together enters gas-cleaning installation and purifies after recirculation blower is got back to circulating fluid bed reactor.
Particle is pressed said process, circulates in the first fluidized bed and reaction of low temperature plasma device.Meanwhile, carry out charging mentioned above, operations such as preheating particulate in second fluidized-bed.After the total reaction time of particle in the first fluidized bed and reaction of low temperature plasma device reaches 1.5h, PVC draws off reactor with products C, after the degassing, adopts oxygen flask combustion method (GB 9872-1988) to record in the CPVC feed bin, cl content 69.56% meets the CPVC production requirement.
Embodiment 4
Median size is the PVC particle of 150 μ m, and by the charging bole first fluidized bed of packing into, charge amount is 1 ton.The ON cycle blower fan is with Cl
2Concentration is 50% Cl
2/ Ar mixed gas feeds fluidized-bed, and the unlatching stirring makes PVC particle active fluidization.Add heated oil in chuck, particle heats up gradually from 60 ℃, and keeping the interior PVC particle temperature of fluidized-bed is 100 ℃.The control valve of opening between the first fluidized bed and low-temperature plasma descending-bed reactor makes the PVC particle enter the low-temperature plasma descending-bed reactor, and riser reactor, causes chlorination in the low-temperature plasma tagma.Riser tube and descending bed are operated under normal pressure, and temperature is 60 ℃, particle residence time 20s.The solid PVC particle is got back to the first fluidized bed through gas solid separation, finishes the primary particle circulation.The residence time of particle in fluidized-bed is 10min.The reaction end gas of gas after the separation and first fluidized bed output together enters gas-cleaning installation and purifies after recirculation blower is got back to circulating fluid bed reactor.
Particle is pressed said process, circulates in the first fluidized bed and reaction of low temperature plasma device.Meanwhile, carry out charging mentioned above, operations such as preheating particulate in second fluidized-bed.After the total reaction time of particle in the first fluidized bed and reaction of low temperature plasma device reaches 2h, PVC draws off reactor with products C, after the degassing, adopts oxygen flask combustion method (GB 9872-1988) to record in the CPVC feed bin, cl content 68.09% meets the CPVC production requirement.
Claims (5)
1. the device of a low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride, it is characterized in that: this device comprises:
A, one are used for storing and preliminary preheating material PVC particulate polyvinyl chloride particles feed bin (11);
B, two first class bed bioreactors (7A) that are arranged in juxtaposition and second fluidized-bed reactor (7B), two reactors are connected with polyvinyl chloride particles feed bin (11) by carrier pipe respectively;
C, a descending-bed reactor (13), this descending-bed reactor are connected with the bottom of two fluidized-bed reactors by the pipeline that has control valve respectively, in this descending-bed reactor inside low-temperature plasma generating unit (3) are housed;
D, two first riser reactors (4A) that are arranged in juxtaposition and second riser reactor (4B), the bottom of two riser reactors is connected with the bottom of descending-bed reactor by the pipeline that has control valve respectively, the top of two riser reactors is connected with the top of two fluidized-bed reactors by gas-solid separator (6) respectively, in each riser reactor inside low-temperature plasma generating unit (3) is housed all;
E, two hydrogenchloride that are used for removing reaction end gas, make the pipeline of the chlorine recycle in the system, this pipeline comprises that an exhaust gas cleaner (1) and two are respectively applied for and carries riser tube to carry the recirculation blower (2A) of gas and the recirculation blower (2B) of transferring raw material gas;
F, one are used to store product, and possess the chlorinated polyvinyl chloride feed bin (12) of degassing function.
2. according to the device of the described a kind of low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride of claim 1, it is characterized in that: be provided with stirring rake (9) in described two fluidized-bed reactors that are arranged in juxtaposition.
3. the device of low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride according to claim 1 is characterized in that, described low-temperature plasma is dielectric barrier discharge plasma, radio-frequency plasma or microwave plasma; The discharge mode of low-temperature plasma comprises two kinds of intermittent discharge and continuous discharges.
4. the method for the low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride that installs according to claim 1 of an employing is characterized in that this method may further comprise the steps:
1) after the PVC particle is preheated to 60～80 ℃ in the polyvinyl chloride particles feed bin, at first joins in one of them fluidized-bed reactor;
2) feed unstripped gas in the fluidized-bed reactor after adding the PVC particle, the PVC particle is reacted with unstripped gas in fluidized-bed reactor, temperature of reaction is 60～140 ℃, and the residence time is 5～30min, and the operation absolute pressure is 0.1atm～1.5atm; The service temperature of PVC particle in riser reactor and descending-bed reactor is 20～140 ℃, and the residence time is 0.1s～2min, and the operation absolute pressure is 0.1atm～1atm; In riser reactor and descending-bed reactor, the power density of low-temperature plasma is 0.1～10W/cm
3
3) reacted PVC particle flows out from the bottom of fluidized-bed reactor, enter the bottom of riser reactor through descending-bed reactor, under the effect of riser tube conveying gas, enter the gas-solid separator on fluidized-bed reactor top, get back in the fluidized-bed reactor, realize the particle circulation;
4) tail gas after unstripped gas and PVC particle react, and riser tube carries gas and the tail gas of PVC particle after gas solid separation to flow out from the fluidized-bed reactor top, enter exhaust gas cleaner except that behind the de-chlorine hydride, enter fluidized-bed reactor and riser reactor recycle through recirculation blower;
5) after the reaction times reaches 30min～4h, the chlorinated polyvinyl chloride product in the fluidized-bed reactor enters the chlorinated polyvinyl chloride feed bin, at 60～80 ℃ of 1～2h that outgas down; Close first descending control valve, the first riser tube control valve, first riser tube conveying gas control valve and the first unstripped gas control valve simultaneously; Open second descending control valve, the second riser tube control valve, second riser tube conveying gas control valve, the second unstripped gas control valve then; Repeating step 1 in another fluidized-bed reactor) to 3).
5. according to the method for the low-temperature plasma circulating fluidize bed continuous production chlorinated polyvinyl chloride described in the claim 4, it is characterized in that: described unstripped gas is the gas mixture of chlorine or chlorine and rare gas element; It is the gas mixture of chlorine, rare gas element or chlorine and rare gas element that riser tube is carried gas.
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| CN103497264A (en) * | 2013-09-29 | 2014-01-08 | 中国平煤神马能源化工集团有限责任公司 | Reaction system and method for intermittent production of chlorinated polyvinyl chloride |
| CN105198034A (en) * | 2015-08-13 | 2015-12-30 | 江苏省环境科学研究院 | Motor regulation and control underwater dense bubble dielectric barrier discharge reactor |
| CN106749784A (en) * | 2016-12-14 | 2017-05-31 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of chlorinated high polymers production technology and device for coupling chemical industry for making chlorine and alkali |
| CN107417814A (en) * | 2017-06-16 | 2017-12-01 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of chlorinated high polymers process units and technique for controlling reacting gas concentration respectively |
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