CN102517062A - Method for preparing hydrocarbon type oil and hydrochloric acid through pyrolytic-catalytic plastic and device - Google Patents
Method for preparing hydrocarbon type oil and hydrochloric acid through pyrolytic-catalytic plastic and device Download PDFInfo
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- CN102517062A CN102517062A CN2011103660279A CN201110366027A CN102517062A CN 102517062 A CN102517062 A CN 102517062A CN 2011103660279 A CN2011103660279 A CN 2011103660279A CN 201110366027 A CN201110366027 A CN 201110366027A CN 102517062 A CN102517062 A CN 102517062A
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Abstract
The invention discloses a method for preparing hydrocarbon type oil and hydrochloric acid through pyrolytic-catalytic plastic and a device. The method comprises the following steps of: crushing waste plastic containing chlorine, feeding into a low-temperature fluidized bed through a spiral feeder, leading the plastic to generate low-temperature pyrolysis under the atmosphere of N2 in the bed, separating out the chlorine in the plastic in a form of HCI (Hydrogen Chloride) gas, entering a washing tower after the HCI gas is separated by a cyclone separator and being absorbed in the washing tower to prepare the hydrochloric acid; and leading solid residues generated by the low-temperature pyrolysis into a high-temperature fluidized bed through a reefed line, introducing mixed gas of N2/O2 into the high-temperature fluidized bed, carrying out combustion and heat release on a part of hydrocarbon residues and O2, pyrolyzing the unreacted solid residues under the high-temperature anoxic atmosphere to generate macromolecule gaseous hydrocarbons, entering a catalyst bed after the macromolecule gaseous hydrocarbons are subjected to gas-solid separation, generating micromolecule hydrocarbons under the action of a catalyst and obtaining the various hydrocarbon type oil after condensation and fractionation.
Description
Technical field
The present invention relates to the method and apparatus of a kind of pyrolysis-catalysis plastics, relate in particular to a kind of pyrolysis-catalysis plastic containing chlorine and produce the method and apparatus of hydrocarbon-type oil and hydrochloric acid.
Background technology
Along with developing rapidly of plastics industry; The application of plastics is also more and more wider; The extensive application of plastics; The usage quantity of for example a large amount of packing plastics films, plastics bag and disposable nondegradable plastic tableware is increased sharply, and brings many whiles easily in the life of giving people, has also caused very serious white pollution.The a large amount of plastic garbage that produces in the daily life is needed badly and is taked efficient manner to handle, and should reduce environmental pollution as far as possible, reaches the purpose of minimizing again.
At present, adopting cracking waste plastics to produce hydrocarbon-type oil is the effective way that reclaims plastic waste, plastics pollution.Cracking system oil has thermo-cracking, catalytic pyrolysis, three kinds of modes of pyrolysis-catalysis.The thermo-cracking less investment; Technology is simple, but long reaction time, production technique is coarse, product is mixed and disorderly, oil yield is low, high, the poor quality of wax content in the gained fuel oil; Be mainly the hydrocarbons of boiling spread broad, wherein gasoline fraction and diesel oil distillate content are not high.The speed of reaction of catalytic pyrolysis is fast, and technology is comparatively simple, invests less; But a large amount of sedimentation of coke are arranged in catalyst surface in the reaction process, make catalyst deactivation, so catalyst levels is big; And the residue after the cracking and catalyst mix are together, are unfavorable for the separation and the recovery of catalyzer.The oil product of the hydrocarbon-type oil that pyrolysis-catalysis method obtains is best, and overcome thermo-cracking and made gasoline and the not high shortcoming of diesel quality, and also this method flexible operation, working cost is low, and catalyst levels is few, and can repeatedly use.So pyrolysis-catalysis method is considered to a kind of method of comparatively ideal treatment of waste plastics.
But conventional pyrolysis-catalysis method is in single reactor drum, to carry out when the pyrolysis plastic containing chlorine; Have single temperature range, during the SE that the pyrolysis chlorinity is bigger (PVC) plastics, include a large amount of HCl gas in the gaseous product; Not only conversion unit there is serious corrodibility, and causes catalyst deactivation, influence the work-ing life of catalyzer; Also influence the oil quality after the catalytic cracking of pyrolysis gas; Therefore the mixed plastic general requirement does not contain plastic containing chlorine, and perhaps mixed plastic will carry out pre-treatment, to slough PVC plastics wherein.
Different with the pyrolysis-catalysis method of routine is patent " is made the method for hydrocarbon ils " with the waste polyolefine plastics (patent No.: CN96116917.6) adopted the method that low temperature pyrogenation combines with high temperature pyrolysis in the single cracking still.After waste and old plastic containing chlorine adds cracking still, carry out the low temperature pyrogenation of plastics earlier, TR is 150-250 ℃, produces HCl gas at this temperature range generation dechlorination reaction; Open the valve that leads to the absorption tower then, close the valve towards catalyst chamber, HCl gas is absorbed the tower absorption and processes hydrochloric acid; After low temperature pyrogenation was accomplished, switch valve was closed the valve towards the absorption tower; Open the valve that leads to catalyst chamber, Pintsch process begins, and Heating temperature is to 400-500 ℃; Cracking produces hydrocarbon gas, and hydrocarbon gas gets into catalytic bed further catalytic pyrolysis under the effect of catalyzer and produces the small molecules splitting gas, and the small molecules splitting gas obtains petrol and diesel oil through condensation, fractionation.This technology has solved the problem of hcl corrosion equipment in the product, can access certain vapour, diesel oil, but still has following point:
(1) the cracking still pyrolytic process intermittently carries out, and carries out low temperature pyrogenation earlier, just can carry out high temperature pyrolysis after low temperature pyrogenation is accomplished, and can not carry out synchronously, and causing can only intermittent feed, and the pyrolysis amount of plastics is limited, and the pyrolytic cycle is long, inefficiency;
Need frequent switch valve when (2) low temperature pyrogenation and high temperature pyrolysis replace, bring some inconvenience, the degree that also more difficult controlling reaction time and reaction are carried out limits its industrial application to a certain extent;
(3) cracking still is arranged in the flue, absorbs fume afterheat, and for pyrolysis provides heat, but easy dust stratification of cracking still outer wall and coking in case coking causes heat transfer deterioration, increase heat transmission resistance, and shortage of heat in the still influences pyrolytic and carries out, and needs regular cleaning.
Summary of the invention
Technical problem: but the pyrolysis-catalysis plastics that the invention provides a kind of simple and effective operate continuously are produced the method and apparatus of hydrocarbon-type oil and hydrochloric acid.
Technical scheme: pyrolysis of the present invention-catalysis plastics are produced the method for hydrocarbon-type oil and hydrochloric acid; With the waste or used plastics raw material after crusher in crushing; Sending into prepackage by screw feeder has in the low temperature fluidized-bed of silica sand; Said waste or used plastics raw material comprises SE and auxiliary material, and said auxiliary material is any or combination of Vilaterm, Vestolen PP 7052, PS;
When pyrolysis starts, from the nitrogen inlet feeding N of low temperature fluidized-bed bottom
2Heating bed temperature to 200～350 ℃, dechlorination reaction takes place in the waste or used plastics raw material in the low temperature fluidized-bed, and the gas-solid two phase products that reaction produces comprise a part of solid residue; Gas-solid two phase products are delivered to the low temperature cyclonic separator to be separated; Isolated solid residue turns back in the low temperature fluidized-bed through first material returning device, and the gas of the isolating HCl of containing gets into washing tower and is prepared into hydrochloric acid, gets into the N in the gas wash tower
2Overflow from the washing tower outlet, after the blower fan supercharging, in the salty new entering low temperature fluidized-bed of nitrogen reflux of low temperature fluidized-bed bottom, realize N
2Circulation;
A part of solid residue in the low temperature fluidized-bed gets into high temperature fluidized bed through second material returning device; Nitrogen and volumetric concentration are after 4%～10% oxygen mixes in gas preheater and is preheated to 300 ℃; Through the combi inlet port of high temperature fluidized bed bottom send into high temperature fluidized bed in; High temperature fluidized bed temperature is increased to 400～500 ℃; The gas-solid two phase products that reaction produces are delivered to high temperature cyclone separator to be separated, and the solid separated particle turns back in the low temperature fluidized-bed through the 3rd material returning device, and isolating macromole gaseous hydrocarbons gets into catalytic bed and produces hydrocarbon-type oil.
Among the present invention, the ash discharging hole that the high temperature fluidized bed middle ash content that produces is provided with from high temperature fluidized bed bottom is discharged.
The hydrocarbon-type oil of producing among the present invention does; The macromole gaseous hydrocarbons gets into the catalytic bed that prepackage has catalyzer from the catalytic bed inlet mouth; The heatable catalytic bed makes temperature rise to 300～380 ℃, macromole gaseous hydrocarbons catalytic pyrolysis be behind the small molecule hydrocarbon successively through the catalytic bed air outlet, the condensing surface inlet mouth gets into the heat release of condensing surface internal cooling, the higher heavy gas oil of fusing point condenses earlier; Flow out from the heavy gas oil outlet; All the other condensation products after the fractionation, successively obtain gasoline, solar oil and some non-condensable gasess according to fusing point successively in condensing surface discharge port, separation column import entering separation column, separate from the separation column outlet.
Catalyzer among the present invention is any of clay mineral, HZSM-5, alkene soil Y zeolite.
Pyrolysis of the present invention-catalysis plastics are produced the device of hydrocarbon-type oil and hydrochloric acid, comprise low temperature fluidized-bed, high temperature fluidized bed, first material returning device, washing tower, second material returning device, low temperature cyclonic separator, high temperature cyclone separator, the 3rd material returning device, catalytic bed, condensing surface, separation column, N
2Source of the gas, O
2Source of the gas and gas preheater;
The low temperature fluidized-bed is isodiametric fluidized-bed; Be provided with low temperature fluidized-bed discharge port at an upper portion thereof; The bottom is provided with the first returning charge import of low temperature fluidized-bed, low temperature fluidized-bed opening for feed, the returning charge outlet of low temperature fluidized-bed and the second returning charge import of low temperature fluidized-bed; The bottom is provided with nitrogen reflux mouth and nitrogen inlet; Said low temperature fluidized-bed discharge port is connected with the import of low temperature cyclonic separator, and low temperature cyclonic separator air outlet is connected with washing tower inlet mouth on the washing tower through pipeline, and the solid separating opening of low temperature cyclonic separator passes through first material returning device and is connected with the first returning charge import; Also be provided with hydrochloric acid outlet on the washing tower and be connected said nitrogen inlet and N with the nitrogen reflux mouth through blower fan with, said nitrogen outlet
2Source of the gas connects;
High temperature fluidized bed is isodiametric fluidized-bed; Be provided with high temperature fluidized bed discharge port at an upper portion thereof; The bottom is provided with high temperature fluidized bed opening for feed; The bottom is provided with ash discharging hole and combi inlet port, and said high temperature fluidized bed opening for feed is connected with low temperature fluidized-bed returning charge outlet through second material returning device, and said high temperature fluidized bed discharge port is connected with high temperature cyclone separator; The high temperature cyclone separator air outlet is connected with catalytic bed inlet mouth on the catalytic bed through pipeline, and the solid separating opening of high temperature cyclone separator passes through the 3rd material returning device and is connected with the second returning charge import of low temperature fluidized-bed; Said combi inlet port through gas preheater respectively with N
2Source of the gas and O
2Source of the gas connects;
Catalytic bed air outlet on the catalytic bed is connected with condensing surface inlet mouth on the condensing surface through pipeline; Also be provided with cooling water outlet, entrance of cooling water, heavy gas oil outlet and condensing surface discharge port on the condensing surface; Said separation column is provided with separation column import and separation column outlet, and said condensing surface discharge port is connected with the separation column import through pipeline.
Beneficial effect: the present invention compared with prior art has following advantage and marked improvement:
(1) existing pyrolysis-catalysis method all carries out in single reaction vessel, causes containing a large amount of HCl gas in the gaseous product, and is serious to corrosion on Equipment, makes catalyst deactivation easily, oil product of poor quality; Perhaps need switch low temperature pyrogenation and high temperature pyrolysis, intermittent feed brings the inconvenience of operation, inefficiency.The present invention adopts bilayer structure, does not receive the restriction of single cracking still structure, can continuous-feeding; Break through the deficiency of inventing intermittent feeding before this, low temperature pyrogenation and high temperature pyrolysis can carry out simultaneously, not free sequencing; Two temperature also can independently be controlled, and does not need to change bed temperature with the switching of pyrolysis phase, and the pyrolysis amount of plastics increases; Cycle obviously shortens, and pyrolytic efficient improves.
(2) do not need waste and old plastics are carried out pre-treatment, in the low temperature pyrogenation stage, according to the experimental result of thermogravimetric (TGA), the chlorine more than 99.5% can be decomposed and slough, and removal efficiency is high; And behind the HCl gas process washing tower, can be absorbed and process hydrochloric acid, for other chemical technologies are supplied raw materials, and remaining pure N
2Can recirculation use, make material be fully utilized, also can reduce production costs greatly.
(3) low temperature pyrogenation of the present invention is with N
2As the pyrolysis medium; Under the atmosphere of anaerobic, carry out; Can cut off the means of chemical reaction of synthetic Dioxins and furans (PCDD/PCDFS), fundamentally stop the generation of dioxin-like chemical, thereby avoided traditional waste incineration can not effectively remove the drawback of Dioxins.
(4) method of hydrocarbon-type oil is produced in the pyrolysis-catalysis of routine; Compare pyrolysis method and catalytic pyrolysis method, energy consumption is the highest, needs to consume a large amount of outer heat; Cost is higher; The double-fluidized-bed pyrolysis of the present invention adopts silica sand as heat transfer carrier, and hydrocarbon residue burning liberated heat is that high temperature pyrolysis and low temperature pyrogenation provide reaction required heat, through controlling the O of high temperature fluidized bed feeding
2/ N
2Concentration ratio can reach the state of autothermal equilibrium, does not need the outer heat of additive decrementation, and is can loss-rate tradition method of making oil low, and succinct efficient, easy and simple to handle.
Description of drawings
Fig. 1 is the flow process and the structural representation of device that the inventive method adopts;
Have among the figure: 1. crusher; 2. screw feeder; 3. low temperature fluidized-bed; 4. high temperature fluidized bed; 5. first material returning device; 6. washing tower; 7. blower fan; 8.N
2Source of the gas; 9. second material returning device; 10. low temperature cyclonic separator; 11. high temperature cyclone separator; 12. the 3rd material returning device; 13. catalytic bed; 14. condensing surface; 15. separation column; 16.O
2Source of the gas; 17. gas preheater, 31. low temperature fluidized-bed discharge ports, the first returning charge import of 32. low temperature fluidized-beds; 33. low temperature fluidized-bed opening for feed, 34. low temperature fluidized-bed returning charges outlet, the second returning charge import of 35. low temperature fluidized-beds; 41. high temperature fluidized bed opening for feed, 42. high temperature fluidized bed discharge ports.
A. plastics enter the mouth; B. nitrogen reflux mouth; C. nitrogen inlet; D. low temperature cyclonic separator air outlet; E. washing tower inlet mouth; F. hydrochloric acid outlet; G. nitrogen outlet; H. ash discharging hole; I. combi inlet port; J. high temperature cyclone separator air outlet; K. catalytic bed inlet mouth; L. catalytic bed air outlet; M. cooling water outlet; N. entrance of cooling water; O. condensing surface inlet mouth; P. heavy gas oil outlet; Q. condensing surface discharge port; R. separation column import; S. separation column outlet.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described.
The reaction unit that the inventive method adopted is " a kind of based on coal gasification for preparing hydrogen and separation of C O in patent of invention
2Method and device thereof " variation carried out on the basis of (patent No.: CN201010172522 ;) to call this patent in the following text, mainly form by regenerative reactor system and mixing gasifying reactor assembly two portions, this patent is used for coal gasification for preparing hydrogen; adopt varying-arca channel to help the lifting and the purification of hydrogen-rich gas; but as in the plastics pyrolytic reaction of migrating, then can be thinner because of the caliber of fluidized-bed riser tube, pipeline is stopped up by the plastic hot hydrolysis products easily.The device that the present invention adopted is as shown in Figure 1; Be with two variable cross-section fluidized-beds in this patent; Change the single straight tube fluidized-bed of equal diameter pipeline into, transition section no longer is set, with the pyrolysis-catalysis system oil reaction that is applicable to waste and old plastic containing chlorine; Overflow groove and tremie pipe rename material returning device as, and the elswhere of device is constant.
The device that the present invention adopted mainly is made up of crusher 1, screw feeder 2, low temperature fluidized-bed 3, high temperature fluidized bed 4, first material returning device 5, washing tower 6, second material returning device 9, low temperature cyclonic separator 10, high temperature cyclone separator 11, the 3rd material returning device 12, catalytic bed 13, condensing surface 14, separation column 15.
Technological process of the present invention is: will mix waste and old plastic containing chlorine after crusher 1 fragmentation, joining prepackage by screw feeder 2 has in the low temperature fluidized-bed 3 of silica sand, when pyrolysis starts, from the nitrogen inlet C feeding N of low temperature fluidized-bed 3
2, heating bed temperature to 200～350 ℃.Low temperature fluidized-bed 3 is a bubbling fluidized bed, N
2As fluidizing agent; Mix waste and old plastic containing chlorine elementary pyrolysis takes place in bed; Be mainly dechlorination reaction, reaction finishes the back and produces solid residue and a large amount of HCl gas, according to TGA (thermogravimetric) experimental result; Chlorine in the plastics more than 99.5% will be removed, and the gaseous product at low temperature fluidized-bed 3 tops is mainly HCl, N
2And water vapour.Part solid residue mixes formation gas-solid product with gaseous product, the gas-solid product is delivered to low temperature cyclonic separator 10 through low temperature fluidized-bed discharge port 31 to be separated, and isolated solid residue sends back to low temperature fluidized-bed 3 by first material returning device 5; The isolating gas mixture that contains HCl is discharged from low temperature cyclonic separator air outlet; Get into washing tower 6, in washing tower 6, HCl and water vapour are absorbed and prepared into hydrochloric acid; Flow out unabsorbed N from the hydrochloric acid outlet F of washing tower
2Separate from the nitrogen outlet G of washing tower 6, again after blower fan 7 superchargings, send back to again in the low temperature fluidized-bed, realize N from the nitrogen reflux mouth B of low temperature fluidized-bed 3
2Circulation.
The solid residue that obtains after 3 pyrolysis of low temperature fluidized-bed is mainly hydrocarbon polymer, and wherein a part of solid residue gets in high temperature fluidized bed 4 through second material returning device 9.Nitrogen and volumetric concentration are that 4%～10% oxygen mixes in gas preheater 17 and is preheated to 300 ℃, are got in high temperature fluidized bed 4 by the combi inlet port I of high temperature fluidized bed 4 bottoms.High temperature fluidized bed 4 is a circulating fluidized bed, and its temperature is increased to 400～500 ℃, the O in hydrocarbon residue of part and the gas mixture
2Reacted CO
2And emit a large amount of heat, for high temperature pyrolysis provides required heat, reaction finishes back O
2Approach exhaustion causes anoxybiotic atmosphere, and unreacted hydrocarbon polymer fast pyrogenation under high temperature anoxybiotic atmosphere is the macromole gaseous hydrocarbons.The ash-removing mouth H that the ash content that produces in high temperature fluidized bed 4 is provided with from high temperature fluidized bed 4 bottoms discharges; The gas-solid two phase products that reaction produces are after high temperature cyclone separator 11 separates; The solid separated particle turns back in the low temperature fluidized-bed 3 through the 3rd material returning device 12; Isolating macromole gaseous hydrocarbons is discharged from the high temperature cyclone separator air outlet J on high temperature cyclone separator 11 tops, gets into catalytic bed 13.
The macromole gaseous hydrocarbons enters bed from the catalytic bed air inlet K of catalytic bed 13 bottoms, heating bed temperature to 300～380 ℃, and the catalysis that catalytic bed 13 is placed is clay mineral, HZSM-5, alkene soil Y zeolite and metal promoter; Macromole gaseous hydrocarbons catalytic pyrolysis under the effect of catalyzer is a small molecule hydrocarbon; Small molecule hydrocarbon comes out from the catalytic bed air outlet L at catalytic bed 13 tops, gets into condensing surface 14 through condensing surface inlet mouth O again, and condensing surface 14 is provided with entrance of cooling water N and cooling water outlet M; Gas heat release in condensing surface 14; Elder generation's condensation goes out the higher heavy gas oil of fusing point, and the heavy gas oil outlet P from condensing surface flows out, and all the other condensation products are after condensing surface discharge port Q comes out; Get in the separation column 15 by separation column import R; Small molecule hydrocarbon successively obtains gasoline, solar oil and some non-condensable gasess through after the fractionation according to fusing point, and S separates from the separation column outlet.
Round-robin inert support material is a silica sand between low temperature fluidized-bed 3 and high temperature fluidized bed 4, hydrocarbon residue and O in high temperature fluidized bed 4
2The reaction liberated heat; Make the temperature of silica sand raise, the higher silica sand of a part of temperature separates through high temperature cyclone separator 11, is turned back in the low temperature fluidized-bed 3 by the 3rd material returning device 12; The higher silica sand release of heat of temperature is given other bed material; For low temperature pyrogenation provides heat, realize autothermal equilibrium, reach the purpose of the transmission energy of silica sand.
Claims (5)
1. pyrolysis-catalysis plastics are produced the method for hydrocarbon-type oil and hydrochloric acid; It is characterized in that; With the waste or used plastics raw material after crusher (1) fragmentation; Sending into prepackage by screw feeder (2) has in the low temperature fluidized-bed (3) of silica sand, and said waste or used plastics raw material comprises SE and auxiliary material, and said auxiliary material is any or combination of Vilaterm, Vestolen PP 7052, PS;
When pyrolysis starts, from nitrogen inlet (C) the feeding N of low temperature fluidized-bed (3) bottom
2Heating bed temperature to 200～350 ℃, dechlorination reaction takes place in the waste or used plastics raw material low temperature fluidized-bed (3) in, and the gas-solid two phase products that react generation comprise a part of solid residue; Gas-solid two phase products are delivered to low temperature cyclonic separator (10) to be separated; Isolated solid residue turns back in the low temperature fluidized-bed (3) through first material returning device (5), and the gas of the isolating HCl of containing gets into washing tower (6) and is prepared into hydrochloric acid, gets into the N in the gas wash tower (6)
2Overflow from washing tower outlet (G), after blower fan (7) supercharging, the nitrogen reflux mouth (B) bottom low temperature fluidized-bed (3) gets in the low temperature fluidized-bed (3) again, realizes N
2Circulation;
A part of solid residue in the low temperature fluidized-bed (3) gets into high temperature fluidized bed (4) through second material returning device (9); Nitrogen and volumetric concentration are after 4%～10% oxygen mixes in gas preheater (17) and is preheated to 300 ℃; Combi inlet port (I) through high temperature fluidized bed (4) bottom is sent in high temperature fluidized bed (4); The temperature of high temperature fluidized bed (4) is increased to 400～500 ℃; The gas-solid two phase products that reaction produces are delivered to high temperature cyclone separator (11) to be separated, and the solid separated particle turns back in the low temperature fluidized-bed (3) through the 3rd material returning device (12), and isolating macromole gaseous hydrocarbons gets into catalytic bed (13) and produces hydrocarbon-type oil.
2. a kind of pyrolysis according to claim 1-catalysis plastics are produced the method for hydrocarbon-type oil and hydrochloric acid, it is characterized in that, the ash content that produces in high temperature fluidized bed (4) is discharged from the ash discharging hole (H) that high temperature fluidized bed (4) bottom is provided with.
3. a kind of pyrolysis according to claim 1-catalysis plastics are produced the method for hydrocarbon-type oil and hydrochloric acid; It is characterized in that; The described hydrocarbon-type oil of producing does, the macromole gaseous hydrocarbons gets into the catalytic bed (13) that prepackage has catalyzer from catalytic bed inlet mouth (K), and heatable catalytic bed (13) makes temperature rise to 300～380 ℃; Macromole gaseous hydrocarbons catalytic pyrolysis is that (L), condensing surface inlet mouth (O) get into condensing surface (14) internal cooling heat release through the catalytic bed air outlet successively behind the small molecule hydrocarbon; The higher heavy gas oil of fusing point condenses earlier, flows out from heavy gas oil outlet (P), and all the other condensation products get in the separation column (15) after the fractionation through condensing surface discharge port (Q), separation column import (R) successively; Successively obtain gasoline, solar oil and some non-condensable gasess according to fusing point, separate from separation column outlet (S).
4. a kind of pyrolysis according to claim 1-catalysis plastics are produced the method for hydrocarbon-type oil and hydrochloric acid, it is characterized in that, said catalyzer is any of clay mineral, HZSM-5, alkene soil Y zeolite.
5. pyrolysis-catalysis plastics of realizing the said method of claim 1 are produced the device of hydrocarbon-type oil and hydrochloric acid; It is characterized in that, comprise low temperature fluidized-bed (3), high temperature fluidized bed (4), first material returning device (5), washing tower (6), second material returning device (9), low temperature cyclonic separator (10), high temperature cyclone separator (11), the 3rd material returning device (12), catalytic bed (13), condensing surface (14), separation column (15), N
2Source of the gas (8), O
2Source of the gas (16) and gas preheater (17);
Said low temperature fluidized-bed (3) is isodiametric fluidized-bed; Be provided with low temperature fluidized-bed discharge port (31) at an upper portion thereof; The bottom is provided with the first returning charge import (32) of low temperature fluidized-bed, low temperature fluidized-bed opening for feed (33), low temperature fluidized-bed returning charge outlet (34) and the second returning charge import (35) of low temperature fluidized-bed; The bottom is provided with nitrogen reflux mouth (B) and nitrogen inlet (C); Said low temperature fluidized-bed discharge port (31) is connected with the import of low temperature cyclonic separator (10); Low temperature cyclonic separator air outlet (D) is connected with washing tower inlet mouth (E) on the washing tower (6) through pipeline, and the solid separating opening of low temperature cyclonic separator (10) passes through first material returning device (5) and is connected with the first returning charge import (32); Also be provided with on the washing tower (6) hydrochloric acid outlet (F) and, said nitrogen outlet (G) is connected with nitrogen reflux mouth (B) through blower fan (7), said nitrogen inlet (C) is connected with N2 source of the gas (8);
Said high temperature fluidized bed (4) are isodiametric fluidized-bed; Be provided with high temperature fluidized bed discharge port (42) at an upper portion thereof; The bottom is provided with high temperature fluidized bed opening for feed (41); The bottom is provided with ash discharging hole (H) and combi inlet port (I); Said high temperature fluidized bed opening for feed (41) is connected with low temperature fluidized-bed returning charge outlet (33) through second material returning device (9); Said high temperature fluidized bed discharge port (42) is connected with high temperature cyclone separator (11), and high temperature cyclone separator air outlet (J) is connected with catalytic bed inlet mouth (K) on the catalytic bed (13) through pipeline, and the solid separating opening of high temperature cyclone separator (11) passes through the 3rd material returning device (12) and is connected with the second returning charge import (35) of low temperature fluidized-bed; Said combi inlet port (I) through gas preheater (17) respectively with N
2Source of the gas (8) and O
2Source of the gas (16) connects;
Catalytic bed air outlet (L) on the said catalytic bed (13) is connected with condensing surface inlet mouth (O) on the condensing surface (14) through pipeline; Also be provided with cooling water outlet (M), entrance of cooling water (N), heavy gas oil outlet (P) and condensing surface discharge port (Q) on the condensing surface (14); Said separation column (15) is provided with separation column import (R) and separation column outlet (S), and said condensing surface discharge port (Q) is connected with separation column import (R) through pipeline.
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| CN113604244A (en) * | 2021-08-16 | 2021-11-05 | 青岛理工大学 | System and method for in-situ catalytic pyrolysis of waste plastics |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164542A (en) * | 1996-05-07 | 1997-11-12 | 南京理工大学 | Method for preparation of hydrocarbon oil by using waste and old polyolefins |
| CN1392224A (en) * | 2001-06-14 | 2003-01-22 | 上海市环境工程设计科学研究院 | Oil refining process of waste plastic and equipment |
| CN101050372A (en) * | 2007-04-29 | 2007-10-10 | 清华大学 | Method for full constituent utilizing resources of wastes of plastic containing chlorine in fluid bed |
| CN101851523A (en) * | 2010-06-01 | 2010-10-06 | 上海劲飚环保科技有限公司 | Continuous waste plastics refining unit |
| CN202359074U (en) * | 2011-11-17 | 2012-08-01 | 东南大学 | Device for producing hydrocarbon-type oil and hydrochloric acid by pyrolyzing-catalyzing plastics |
-
2011
- 2011-11-17 CN CN201110366027.9A patent/CN102517062B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164542A (en) * | 1996-05-07 | 1997-11-12 | 南京理工大学 | Method for preparation of hydrocarbon oil by using waste and old polyolefins |
| CN1392224A (en) * | 2001-06-14 | 2003-01-22 | 上海市环境工程设计科学研究院 | Oil refining process of waste plastic and equipment |
| CN101050372A (en) * | 2007-04-29 | 2007-10-10 | 清华大学 | Method for full constituent utilizing resources of wastes of plastic containing chlorine in fluid bed |
| CN101851523A (en) * | 2010-06-01 | 2010-10-06 | 上海劲飚环保科技有限公司 | Continuous waste plastics refining unit |
| CN202359074U (en) * | 2011-11-17 | 2012-08-01 | 东南大学 | Device for producing hydrocarbon-type oil and hydrochloric acid by pyrolyzing-catalyzing plastics |
Non-Patent Citations (4)
| Title |
|---|
| JOHN SCHEIRS, WALTER KAMINSKY: "《Feedstock Recycling and Pyrolysis of Waste Plastic：Converting Waste Plastics into Diesel and Other Fuels》", 24 May 2006, WILEY SERIES IN POLYMER SCIENCE * |
| 刘贤响: "废塑料裂解制燃料的研究进展", 《化工进展》 * |
| 李法鸿: "废塑料混合物分段热裂解的研究", 《石油炼制与化工》 * |
| 龙世刚等: "加热方式与载气性质对废弃PVC热解脱氯的影响", 《钢铁》 * |
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| CN108517223A (en) * | 2018-03-29 | 2018-09-11 | 南京大学连云港高新技术研究院 | A kind of preparation method of low chlorine plastic cracking oil |
| CN110358562A (en) * | 2018-04-10 | 2019-10-22 | 杭州润泰新能源设备有限公司 | A kind of reactor for waste plastics conversion |
| CN111330942A (en) * | 2020-02-28 | 2020-06-26 | 上海交通大学 | Low temperature pre-dechlorination method and device for low dioxin thermochemical conversion process |
| CN111330942B (en) * | 2020-02-28 | 2021-11-23 | 上海交通大学 | Low temperature pre-dechlorination method and device for low dioxin thermochemical conversion process |
| CN113604244A (en) * | 2021-08-16 | 2021-11-05 | 青岛理工大学 | System and method for in-situ catalytic pyrolysis of waste plastics |
| CN113604244B (en) * | 2021-08-16 | 2022-08-16 | 青岛理工大学 | System and method for in-situ catalytic pyrolysis of waste plastics |
| CN116409781A (en) * | 2023-03-21 | 2023-07-11 | 重庆科技学院 | Process and device for preparing hydrogen-rich gas and carbon nano tube by PVC catalytic pyrolysis |
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