CN105524642A - Apparatus and method thereof for directly heating and cracking waste polyolefin by oxy-hydrogen combustion method - Google Patents
Apparatus and method thereof for directly heating and cracking waste polyolefin by oxy-hydrogen combustion method Download PDFInfo
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Abstract
The invention relates to the field of cracking of waste polyolefin, and concretely relates to an apparatus and a method thereof for directly heating and cracking waste polyolefin by an oxy-hydrogen combustion method. The apparatus comprises an oxy-hydrogen combustor (1-3) and a pyrolysis reaction apparatus (1-1), the oxy-hydrogen combustor (1-3) is communicated to the pyrolysis reaction apparatus (1-1), the pyrolysis reaction apparatus (1-1) comprises a pyrolysis reactor (2-1), the pyrolysis reactor (2-1) comprises a mixer (2-1a) and a reactor (2-1b) which are connected up and down; an overheated steam inlet (3-1) and a gas-liquid mixing material inlet (3-3) are respectively arranged on two opposite sidewalls of the mixer (2-1a) along the tangential direction, and a gaseous state material inlet (3-2) is arranged at top of the mixer (2-1a) along the axial direction. The apparatus uses a tangential or axial mixing mode of overheated steam and the material to effectively avoid over cracking or incomplete cracking due to uneven mixing.
Description
Technical field
The present invention relates to waste polyolefin cracking field, particularly, the present invention relates to a kind of device and method of oxyhydrogen combustion method direct heating cracking waste polyolefin.
Background technology
Polyolefine belongs to broad-spectrum high-tonage plastics dai product.Have data to show, the plastics consumption of China in 2011 has reached nearly 6,000 ten thousand tons that account for world consumption total amount the last 1/4, becomes the large plastics country of consumption of the first in the world.Meanwhile, because plastics are general shorter for especially plastics packed work-ing life, a large amount of plastic waste causes day by day serious " white pollution ".In plastic waste, usually can reach 60 ~ 70% with the polyolefinic accounting that polyethylene and polypropylene are representative, therefore the process of waste polyolefin becomes a main aspect in Treatment of Waste Plastics.
Landfill, burning and recycling are the main method of Treatment of Waste Plastics both at home and abroad at present.Though landfill and burning disposal still occupy higher share at majority state, along with the growth year by year of plastic waste amount and the increasingly stringent of environmental protection management, landfill and burning disposal start to be challenged.The cost of land of landfill is day by day expensive, even basic optional without ground in some place; Burn the resistance being subject to surrounding resident because of the discharge of poison gas.
The recycling of waste polyolefin is a kind of best mode of sustainable use petroleum resources.Waste polyolefin is reclaimed by Pintsch process the recycle that monomeric olefin can not only realize petroleum hydrocarbon resource, is also expected to expand cracking stock source, alleviates the ubiquitous insufficient raw material problem of current large-scale ethylene plant to a certain extent.
Hydrocarbon pyrolysis is the main stream approach of current preparing small molecule alkene.High reaction temperature and short residence time(SRT) are conducive to improving olefins yield and the generation reducing by product, and this just requires that the reaction of counterincision solution applies the heat supply of very high strength.From the angle of heat transfer, thermo-cracking can be divided into direct heating cracking (Directlyheatedpyrolysis) and indirect heating cracking (Indirectlyheatedpyrolysis), the former refers to that heat is directly passed to cracking stock without heat-transfer medium by thermal source, and latter need by heat-transfer medium (reaction tube wall) to cracking stock transferring heat.Steam cracking (Steamcracking) technology of employing tube cracking furnace is the Typical Representative of indirect heating cracking, and most small-numerator olefin is all adopt this method to produce.As the core of steam cracking technology, tube cracking furnace technology is updated through long-term, and performance is closely perfect.For the reason that the heat transfer deterioration reduced because the coking of boiler tube inwall causes and pressure drop increase, petroleum naphtha is still prevailing cracking stock.
For the object expanding cracking stock source, people propose multiple improvement to cracking technique in recent years, and wherein existing indirect heating cracking technique, also has direct heating cracking technique.
The feature of the cracking technique that US Patent No. 7744747B2, US7578929B2, US6743961B2 etc. announce is the heavy feed stocks such as crude oil to be used for steam cracking, but all need pre-treating technology to be evaporated by light ends wherein, then with pyrolyzer, cracking is carried out to light ends.This has broken away from the constraint of crude oil work flow to cracking operation to a certain extent, but the actual cracking stock used is still the light ends in crude oil, does not expand in fact the source of cracking stock.The feature of the cracking technique that US Patent No. 4136015 and US4256565 announce is high-temperature combustion gas to be used as hot gas carrier, adopts direct heating cracking mink cell focus.Although this type of technology can in cracker By Direct Pyrolysis heavy oil even crude oil, in order to realize high efficient mixed and the rapid cleavage of hot gas carrier and cracking stock, often need by complicated apparatus or other technologies means.
Recently someone proposes selective hydrogen burning technology, changes indirect heating into direct heating, heat scission reaction is carried out in adiabatic reactor, does not need external heat source.Such as Chinese patent CN101875591A, this technology is by selective hydrogen burning catalyst, hydrogen, oxygen and hydrocarbon raw material mixture flow are introduced hydrogen catalysis combustion unit, hydrogen is wherein made to carry out catalyst combustion reaction, logistics heated, the logistics after heating enters adiabatic reaction apparatus generation heat scission reaction.This technology needs multistage hydrogen catalysis combustion unit and adiabatic reaction apparatus series connection to improve olefins yield, and feelings burning needs by catalyzer, necessarily increases cost, and the bad control of process.
Reclaim the object of monomeric olefin for cracking waste polyolefin, it is also proposed multiple single stage method and two-step approach cracking technique in recent years.
The method that the cracking waste plastics that US Patent No. 532691/5136117 is announced reclaims monomer ethylene is typical single stage method cracking, and the solid particulate being heated to high temperature directly contacts with waste polyolefin particle by this method, makes it the cracking that is rapidly heated.In order to obtain high temperature rise rate and good contact heat transfer effect, the granularity of this method to raw material has strict demand.The method that the cracking waste plastics that Chinese patent CN95110364.4, US Patent No. 5639937 and US5731483 etc. announce reclaims monomeric olefin then belongs to two-step approach cracking, namely first under lower cracking temperature, solid plastic waste is converted into liquid cracking stock; Second step is Pintsch process, and liquid starting material is cracked into small-numerator olefin.In above-mentioned patent, second step Pintsch process all adopts traditional tube cracking furnace, and this has quite strict requirement to the liquid cracking stock that the first step produces, and generally liquid cracking stock need be controlled in the scope being equivalent to naphtha fraction.
Summary of the invention
In view of existing cracking waste polyolefin reclaims the deficiency of monomeric olefin technology existence, the object of this invention is to provide a kind of device and technique of two-step approach cracking waste polyolefin.The liquid hydrocarbon that waste polyolefin obtains through the gentle cracking of the first step by the present invention is as cracking stock (hereinafter referred to as cracking stock), and adopt the superheated vapour that oxyhydrogen combustion produces, direct heating cracking stock produces monomer small-numerator olefin.This technique has cracking stock wide material sources, switches flexibly, the advantages such as olefins yield is high, and de-coking operations is simple between raw material.
The invention provides a kind of device of oxyhydrogen combustion method direct heating cracking waste polyolefin, comprise oxy-hydrogen burner 1-3 and Pintsch process reaction unit 1-1, described oxy-hydrogen burner 1-3 is connected with Pintsch process reaction unit 1-1, described Pintsch process reaction unit 1-1 comprises high-temperature pyrolysis reactor 2-1, and described high-temperature pyrolysis reactor 2-1 comprises the mixing tank 2-1a and reactor 2-1b that connect up and down;
Described mixing tank 2-1a and reactor 2-1b is internally connected with removable thermopair 2-13 moving up and down; Described reactor 2-1 internal-response district is connected with quenching apparatus 2-11a moving up and down;
The two side that described mixing tank 2-1a is relative is tangentially respectively arranged with superheated vapour entrance 3-1 and gas-liquid mixed material entrance 3-3, and described mixing tank 2-1a top is in axial direction provided with Gaseous materials entrance 3-2; Wherein said superheated vapour entrance 3-1 is connected with oxy-hydrogen burner 1-3.
Root device of the present invention, also comprises the gentle pyrolyzer 1-5 of polyolefine and is connected with high-temperature pyrolysis reactor 1-1, obtain liquid hydrocarbon for gentle cracking waste polyolefin.
If during the cracking stock liquid hydrocarbon that to be viscosity very large, preheating gasification installation 1-4 can be added in a device, be arranged between high-temperature pyrolysis reactor 1-1 and the gentle pyrolyzer 1-5 of polyolefine.
According to said apparatus, when adding preheating gasification installation 1-4, Gaseous materials entrance 3-2 and the gas-liquid mixed material entrance 3-3 of described mixing tank 2-1a are connected to raw material preheating gasification installation 1-4.
According to said apparatus, described oxy-hydrogen burner 1-3 is connected with decoking regeneration reactor 1-2.
Above-mentioned mixing tank is outside equipped with mixing tank heating and thermal insulation cover 2-24, and described reactor is outside equipped with reaction tubes external thermal insulation 2-4.
Mixing tank in pyrolysis device described above and reactor can be made with stainless steel or other high temperature materials.
Present invention also offers a kind of method of oxyhydrogen combustion method direct heating cracking waste polyolefin, the method is preferably based on the device of above-mentioned cracking waste polyolefin, specifically comprises the following steps:
1) waste polyolefin is carried out gentle cracking and obtain liquid hydrocarbon, using liquid hydrocarbon as cracking stock;
2) hydrogen and oxygen delivery are entered oxy-hydrogen burner, burning generates superheated vapour, makes the temperature range of superheated vapour be 800 ~ 2000 DEG C;
Wherein, between hydrogen and oxygen, mass ratio is 1:5 ~ 1:8, and hydrogen keeps certain excessive;
3) superheated vapour and cracking stock are delivered into Pintsch process reaction unit respectively, superheated vapour and cracking stock are mixed to form scission reaction material rapidly in the mixing zone of Pintsch process reaction unit, and make scission reaction material be warming up to scission reaction temperature 750 ~ 1000 DEG C instantaneously; Wherein, cracking stock after above-mentioned preheating and superheated vapour hybrid mode in mixing zone is: water vapor tangentially enters the mixing zone of Pintsch process reaction unit, and the mixing zone that cracking stock enters Pintsch process reaction unit vertically or tangentially mixes with high-temperature water vapor; Nozzle is set to improve the linear velocity that water vapor enters reactor, to strengthen mixed effect at steam entry place;
The mass ratio of above-mentioned water vapor and cracking stock can be 20:1 ~ 4:1, preferred 10:1 ~ 5:1, specifically can adjust according to different raw materials;
4) there is scission reaction in scission reaction material in the mixing zone and reaction zone of Pintsch process reaction unit, generates split product;
5) by quenching system, the temperature of split product is down to less than 500 DEG C, thus stops the carrying out of scission reaction.
In the technique of direct heating cracking waste polyolefin, raw material and hot gas carrier mix rapidly and realize heat transmission for improving olefins yield, preventing the generation of by product from being very important.In the inventive method, adopt specific input mode (tangential+tangential or tangential+axial) to facilitate high-temperature water vapor to mix with the rapid of raw material, within the extremely short time, realize heat by the transmission of hot gas carrier to cracking stock.Specifically, if cracking stock is gaseous state before entering reaction unit, then adopt axial mode of entrance, if gas-liquid mixed state or liquid state, then adopt tangential mode of entrance.For strengthening mixed effect, arranging nozzle at steam entry, improving water vapor flow velocity, such water vapor enters reactor at a high speed in a tangential manner, forms eddy current, except mixing rapidly with raw material, can also effectively prevent tube wall coking.
According to the method for oxyhydrogen combustion method direct heating cracking waste polyolefin of the present invention, step 1) the gentle cracking of described waste polyolefin, any gentle cracking technique well known in the art can be used to realize, also can preferably use following technical scheme:
A. after being separated the composition removing the easy release obnoxious flavoures such as polyvinyl chloride from waste polyolefin, by the granulation of waste polyolefin plastic crushing, preferable particle size scope 2 ~ 4mm;
B. after waste polyolefin particle being added the gentle pyrolyzer of polyolefine, by airtight for gentle for polyolefine pyrolyzer and with nitrogen (N
2) or other inert gas purge exhausted airs, to ensure that scission reaction is carried out in an inert atmosphere;
C. range of reaction temperature 360 ~ 450 DEG C is set, preferably 390 ~ 420 DEG C, temperature rise rate 2 ~ 20 DEG C of min
-1, open and stir and start heating, stir speed (S.S.) 200 ~ 400rpm.
D., after reaching the temperature of reaction of setting, insulation stop 1 ~ 120min, preferably 20 ~ 90min, makes scission reaction continue to carry out.
E. after reaching above-mentioned soaking time, stop heating, adopt naturally cooling or water jacket chilling to stop scission reaction, obtained liquid hydrocarbon.
The gentle cracking of above-mentioned waste polyolefin and Pintsch process can carry out continuously, the continuous operation of the process of haveing suffered can be realized like this, also gentle cracking can be used first to prepare cracking stock, and then Pintsch process is carried out to the cracking stock of preparation, the strange land operation of two covering devices can be realized like this.
According to the method for cracking waste polyolefin of the present invention, if during the liquid hydrocarbon that to be viscosity very large of the cracking stock after the gentle cracking of waste polyolefin, described step 4) cracking stock is first delivered into preheating gasifying device, in preheating gasifying device, temperature is 200 ~ 600 DEG C, obtains the cracking stock after preheating; Gaseous materials or gas-liquid mixed material is all changed into after described cracking stock preheating; Cracking stock after superheated vapour and preheating is delivered into Pintsch process reaction unit respectively, even if the cracking stock after preheating participates in splitting reaction.
According to the method for cracking waste polyolefin of the present invention, preferably, described step 4) the scission reaction residence time is 0.01 ~ 0.2s.
According to the method for cracking waste polyolefin of the present invention, described waste polyolefin includes but not limited to polyethylene or polypropylene or the mixture of the two.
Described cracking stock is the liquid hydrocarbon of waste polyolefin after gentle cracking, also can be the mixture of this liquid hydrocarbon and one or more petroleum hydrocarbons, described petroleum hydrocarbon includes but not limited to ethane, propane, petroleum gas, petroleum naphtha, gasoline, diesel oil, residual oil and crude oil etc.
According to the method for cracking waste polyolefin of the present invention, described step 3) can use jet apparatus vertically or tangential direction conveying cracking stock and superheated vapour.
According to the method for cracking waste polyolefin of the present invention, described step 2) temperature adjustment can be carried out with the water at low temperature steam that water or scission reaction process reclaim to superheated vapour.
According to the method for cracking waste polyolefin of the present invention, described step 5) quenching system adopt direct water-cooling or indirect water-cooling mode.
According to the method for cracking waste polyolefin of the present invention, step 5) gained split product can enter separation system after cooling and Waste Heat Recovery System (WHRS) are cooled to room temperature.
In the method for above-mentioned cracking waste polyolefin, after Pintsch process reaction unit runs for some time, coking is formed at reactor wall, Pintsch process reaction unit will enter decoking reproducer, and the connection of Pintsch process reaction unit and oxy-hydrogen burner switches to the connection of decoking regeneration reactor (decoking regeneration reactor here can be same equipment with Pintsch process reaction unit) and oxy-hydrogen burner.Superheated vapour delivers into decoking regeneration reactor, and the temperature of adjustment superheated vapour, makes de-coking operations temperature control at 900 ~ 1100 DEG C.The gas make-up that decoking produces enters hydrogen generating system, produces hydrogen.The decoking time is relevant with reactor inside diameter size, and current experiment room reactor inside diameter is 30mm, does not need coke cleaning on having run two months, that is, suitably increases reactor inside diameter, can also extend the coke cleaning time.Decoking object of the present invention, the first remove tube wall remain, make reaction unaffected, its two, Jiao can be converted into the valuable gases such as hydrogen.Generally start after two months in Pintsch process reaction, switch to decoking program.Above-mentioned switching is realized by valve, when handover is needed, closes material inlet valve, opens decoking water vapor valve.
There is following reaction in decoking:
C+H
2o (gas)=CO+H
2(high temperature)
The air temperature ranges that above-mentioned decoking reproducer generates is 200 ~ 400 DEG C.
According to the method for cracking waste polyolefin of the present invention, described decoking system, cooling system waste heat can reclaim for adjusted hot water and steam temperature out.
The invention has the beneficial effects as follows:
1. in the method for the invention, the superheated vapour produced by oxyhydrogen combustion provides heat for scission reaction, and for whole reactive system, this process is adiabatic process, thus avoids heat transfer process complicated in steam cracking process process;
2. in the methods of the invention, utilize the tangential or axial backmixing mode of superheated vapour and material, can effectively avoid mixing uneven bring cross cracking or cracking incomplete;
3. in the methods of the invention, different feeds mode can be taked for the characteristic of raw material, thus realize carrying out temperature control to different material scission reaction.
Accompanying drawing explanation
Fig. 1 is the schema of cracking waste polyolefin of the present invention.
Fig. 2 is Pintsch process system schematic of the present invention.
Fig. 3 is high-temperature pyrolysis reactor schematic diagram of the present invention; Wherein, A mixing tank section, B, C, D are respectively the upper, middle and lower section of reactor.
Fig. 4 is high-temperature pyrolysis reactor mixing section schematic diagram of the present invention.
Fig. 5 is high-temperature pyrolysis reactor mixing section vertical view of the present invention (containing gas-liquid mixture material entrance).
Fig. 6 is high-temperature pyrolysis reactor mixing section vertical view (containing gaseous state material inlet) of the present invention.
Reference numeral
1-1: Pintsch process reaction unit 1-2: decoking regeneration reactor 1-3: oxy-hydrogen burner
1-4: preheating gasifying device 1-5: the gentle pyrolyzer 1-6 of polyolefine: quenching system
1-7: cooling and Waste Heat Recovery System (WHRS) 1-8: hydrogen make-up 1-9: oxygen
1-10: cracking superheated vapour 1-11: decoking superheated vapour
1-12: the cracking stock 1-13 after preheating: purge and carrier gas 1-14: liquid condition petroleum hydrocarbon
1-15: the liquid hydrocarbon that gentle cracking obtains
1-16: waste polyolefin 1-17: splitting gas 1-18: waste heat recovery water
1-19: temperature adjustment pure water 1-20: splitting gas goes separation system
1-21: hydrogen generating system 1-22: the direct feed path of liquid hydrocarbon
1-23: parallel feeding path 1-24: hydrogen generating system hydrogen 1-25: the gas that decoking produces
2-1: Pintsch process reaction unit 2-1a: mixing tank 2-1b: reactor
2-2: reaction tubes 2-3: the additional heated filament 2-4 of reaction tubes: reaction tubes external thermal insulation
2-5: raw material storage tank 2-6: deionized water storage tank 2-7: feedstock pump
2-8: peristaltic pump 2-9: raw material preheating stove
2-10: superheated vapour producer 2-11a: quenching apparatus 2-11b: condensing works
2-12: instrument temperature controller 2-13: moveable thermopair
2-14: raw material injection port thermopair 2-15: preheating oven thermopair 2-16: circuit heating thermopair
2-17: vapor-liquid separation tank 2-18: gas meter 2-19: gas sampling analysis
2-20: gas emptying 2-21: cooling water outlet
2-22: sweeping gas mass flow controller 2-23: material circuit heating and thermal insulation cover
2-24: mixing tank heating and thermal insulation cover 2-25: quenched water water outlet 2-26: quenched water is intake
3-1: superheated vapour entrance 3-2: Gaseous materials entrance 3-3: gas-liquid mixed material entrance.
Embodiment
Openly in this specification sheets to obtain arbitrary feature, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.Unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.Describedly be only used to help and understand the present invention, should not be considered as concrete restriction of the present invention.
As shown in Figure 1, the method for oxyhydrogen combustion method direct heating cracking waste polyolefin of the present invention, comprises the following steps:
1) waste polyolefin is carried out gentle cracking and obtain liquid hydrocarbon, using liquid hydrocarbon as cracking stock;
2) cracking stock is delivered into preheating gasifying device 1-4 by purging and carrier gas 1-13, in preheating gasifying device 1-4, temperature is 200 ~ 600 DEG C, the cracking stock 1-12 after the preheating of steam state or vapour-liquid mixed state is all changed into (when cracking stock is the very large liquid hydrocarbon of viscosity after cracking stock preheating, carry out this step, if it is very little that cracking stock is viscosity, can not preheating participate in step 4 directly));
3) hydrogen (hydrogen make-up 1-8) and oxygen 1-9 are delivered into oxy-hydrogen burner 1-3, burning generates cracking superheated vapour 1-10, the available appropriate heat recovery water 1-18 or temperature adjustment pure water 1-19 that crosses carries out temperature adjustment to superheated vapour, the temperature range making superheated vapour is 800 ~ 2000 DEG C, allows to there is excess hydrogen in superheated vapour.
4) by superheated vapour and step 2) cracking stock 1-12 after the preheating that obtains delivers into Pintsch process reaction unit 1-1 respectively, cracking stock 1-12 after cracking superheated vapour 1-10 and preheating is mixed to form scission reaction material rapidly in the mixing zone of Pintsch process reaction unit 1-1, and makes scission reaction material be warming up to scission reaction temperature 750 ~ 1000 DEG C instantaneously; Wherein, cracking stock after above-mentioned preheating and superheated vapour hybrid mode in mixing zone is: water vapor tangentially enters the mixing zone of Pintsch process reaction unit, and the mixing zone that the cracking stock after preheating enters Pintsch process reaction unit vertically or tangentially mixes with high-temperature water vapor;
5) there is scission reaction in scission reaction material in the mixing zone and reaction zone of Pintsch process reaction unit, generates split product (i.e. splitting gas 1-17); The scission reaction residence time is 0.01 ~ 0.2s; By the adjustment ratio of material flow, cracking stock and water vapor, the position of quenching apparatus 1-6, can adjust cracking reaction time;
6) by quenching system 1-6, the temperature of split product is down to less than 500 DEG C, thus stops the carrying out of scission reaction.
Step 6) gained split product can through cooling and Waste Heat Recovery System (WHRS) 1-7 be cooled to room temperature after enter separation system 1-20.
In the method for above-mentioned cracking waste polyolefin, waste polyolefin 1-16 is first cracked into waste polyolefin cracking product liquid (i.e. gentle cracking obtain liquid hydrocarbon 1-15) by the gentle pyrolyzer 1-5 of polyolefine, waste polyolefin cracking product liquid is as cracking stock, directly can be entered in preheating gasification installation 1-4 by liquid hydrocarbon direct-path 1-22 and carry out preheating, also can by parallel feeding path 1-23 by liquid hydrocarbon and petroleum hydrocarbon parallel feeding.
In the method for above-mentioned cracking waste polyolefin, after Pintsch process reaction unit 1-1 runs for some time, coking is formed at reactor wall, Pintsch process reaction unit 1-1 will enter decoking reproducer, and Pintsch process reaction unit-1 switches to the connection of decoking regeneration reactor 1-2 and oxy-hydrogen burner 1-3 with the connection of oxy-hydrogen burner 1-3.Superheated vapour delivers into decoking regeneration reactor 1-2, and the temperature of adjustment superheated vapour, makes de-coking operations temperature control at 900 ~ 1100 DEG C.The gas 1-25 temperature range that decoking produces is 200 ~ 400 DEG C, can supplement and enter hydrogen generating system 1-21, generates hydrogen generating system hydrogen 1-24.Described hydrogen generating system hydrogen 1-24 can enter the preparation that oxy-hydrogen burner 1-3 participates in superheated vapour.
Above-mentioned decoking system, cooling system waste heat can reclaim for adjusted hot water and steam temperature out.
As shown in Figure 2,3, device for above-mentioned oxyhydrogen combustion method direct heating cracking waste polyolefin of the present invention, comprise oxy-hydrogen burner 1-3, preheating gasification installation 1-4 and Pintsch process reaction unit 1-1, described oxy-hydrogen burner 1-3 is connected with oxy-hydrogen burner 1-3 respectively with preheating gasification installation 1-4, described Pintsch process reaction unit 1-1 comprises high-temperature pyrolysis reactor 2-1, and described high-temperature pyrolysis reactor 2-1 comprises the mixing tank 2-1a and reactor 2-1b that connect up and down; Described mixing tank 2-1a and reactor 2-1b is internally connected with thermopair 2-13 moving up and down; Described reactor 2-1 internal-response district is connected with quenching apparatus 2-11a moving up and down; The two side that described mixing tank 2-1a is relative is tangentially respectively arranged with superheated vapour entrance 3-1 and gas-liquid mixed material entrance 3-3, and described mixing tank 2-1a top is in axial direction provided with Gaseous materials entrance 3-2; Wherein said superheated vapour entrance 3-1 is connected with oxy-hydrogen burner 1-3.
If during the cracking stock liquid hydrocarbon that to be viscosity very large, preheating gasification installation 1-4 can be added in a device, is connected with high-temperature pyrolysis reactor 1-1.When adding preheating gasification installation 1-4, Gaseous materials entrance 3-2 and the gas-liquid mixed material entrance 3-3 of described mixing tank 2-1a are connected to raw material preheating gasification installation 1-4.
Particularly, described high-temperature pyrolysis reactor 2-1 comprises mixing tank 2-1a and reactor 2-1b, and reactor 2-1b is by reaction tubes 2-2 (bore 30mm), and reaction tubes externally heated oven silk 2-3, reaction tubes pipe Surgery therapy cover 2-4 is formed.As shown in Figure 3, in pyrolysis device, mixing tank is provided with a heating zone (A), and reactor is provided with three heating zone (B, C, D), and the effect of heating zone avoids the excess calories of cracking reactor to scatter and disappear.The mixing tank upper end of high-temperature pyrolysis reactor is connected with feeding pipe.Raw material injection port thermopair 2-14 is provided with, for measuring feeding temperature at opening for feed.Feeding pipe is connected with raw material preheating stove 2-9, and for avoiding the cracking stock of having vaporized again to cool, outside this section of pipeline, be provided with material circuit heating and thermal insulation cover 2-23, circuit heating thermopair 2-16 is for monitoring line temperature.Cracking stock is placed in raw material storage tank 2-5, and use feedstock pump 2-7 that cracking stock is delivered to preheating oven 2-9, cracking stock heats and vaporizes by preheating oven.Deionized water is placed in deionized water storage tank 2-6, uses peristaltic pump 2-8 deionized water to be delivered into superheated vapour producer 2-10 (i.e. oxy-hydrogen burner 1-3).Superheated vapour generator exports is directly connected with high-temperature pyrolysis reactor.For making scission reaction carry out under an inert atmosphere, be connected with noble gas pipeline in feeding pipe side, sweeping gas treatment flow director 2-22, as nitrogen mass flow controllers, controls nitrogen flow at purging and step of reaction.Being provided with quenching apparatus 2-11a, 2-25 moving up and down in cracking reactor is quenched water water inlet, and 2-26 is quenched water water outlet.Also be provided with moveable thermopair 2-13 in cracking reactor can move up and down, for the temperature in assaying reaction district.Mix rapidly with the superheated vapour tangentially entered in a mixer after cracking stock vaporization and reach scission reaction temperature, and cause scission reaction.Quenching apparatus can cool reaction mass in very short time, and the carrying out of termination reaction.The mixture flow of reaction product and water vapor is discharged from reactor lower end, and be cooled to room temperature through condensing works 2-11b, gaseous product is through gas meter 2-18 metered flow.Gas sampling mouth 2-19 is used for sampling test in process.Splitting gas is discharged through gas emptying 2-20.Water of condensation and product liquid are discharged by vapor-liquid separation tank 2-17 lower end cooling water outlet 2-21.Above-mentioned each thermopair of device of the present invention is all connected with instrument temperature controller 2-12, controls for temperature.
The present invention adopts the hybrid mode shown in Fig. 4-6, and the cracking stock of namely vaporizing enters mixing tank vertically through Gaseous materials entrance 3-2, and superheated vapour tangentially enters mixing tank by superheated vapour entrance 3-1.Fig. 5 is applicable to the charging of viscosity higher cracking stock, and namely gas-liquid mixed raw material tangentially enters mixing tank by gas-liquid mixed material entrance 3-3, mixes with the same superheated vapour tangentially entered.
The Pintsch process of the gentle cracking product liquid of embodiment 1 waste polyolefin
The present embodiment waste polyolefin used is high density polyethylene(HDPE)/polypropylene miser, and described cracking stock is the boiling point <380 DEG C cut obtained after the gentle split product distillation of high density polyethylene(HDPE)/polypropylene miser.Gentle cracking adopts 1L capping still, setting cracking temperature 400 DEG C, temperature rise rate 3 ~ 5 DEG C of min
-1, the constant temperature residence time 40 ~ 90min.Boiling point <380 DEG C cut is got in the product liquid distillation gentle cracking obtained.The present embodiment cleavage method used and device as described above.
The present embodiment carries out Pintsch process to cracking stock under the conditions shown in Table 1.The present embodiment cracking result is shown in table 2.
As can be seen from Table 2, polyolefine lysate has good cracking performance, the ethene of acquisition and the molar content of propylene higher.Along with the raising of cracking temperature, ethene, propylene generating rate increase.
The Pintsch process condition of table 1 embodiment 1
The Pintsch process result of table 2 embodiment 1
The Pintsch process of the gentle cracking wax-like products of embodiment 2 waste polyolefin and solar oil mixture
The present embodiment waste polyolefin used is high density polyethylene(HDPE)/polypropylene miser, and described cracking stock is the mixture that the thickness soft solid shape paraffin that obtains of the gentle cracking of high density polyethylene(HDPE) and solar oil are formed by a certain percentage.Gentle cracking adopts 1L capping still, setting cracking temperature 400 DEG C, temperature rise rate 3 ~ 5 DEG C of min
-1, the constant temperature residence time.The present embodiment solar oil used is with embodiment 2, and the Pintsch process system of employing is with embodiment 1.
The present embodiment carries out Pintsch process to cracking stock under the conditions shown in Table 3.The present embodiment cracking result is shown in table 4.
Table 4 shows, and wax-like products mixes with petroleum hydrocarbon and has good crack characteristic, and because the carbon number distribution of wax-like products is comparatively concentrated, and productive rate is higher, and more poly conversion of olefines can have been made like this to be low-carbon alkene.But the blending ratio of wax-like products and petroleum hydrocarbon is unsuitable too high, is generally no more than 50% (mass percentage).
The Pintsch process condition of table 3 embodiment 3
The Pintsch process result of table 4 embodiment 3
Non-elaborated part of the present invention belongs to techniques well known.
Certainly; the present invention can also have various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art can openly make various corresponding change and distortion according to of the present invention, but these change accordingly and are out of shape the protection domain that all should belong to claim of the present invention.
Claims (16)
1. the device of an oxyhydrogen combustion method direct heating cracking waste polyolefin, comprise oxy-hydrogen burner (1-3) and Pintsch process reaction unit (1-1), described oxy-hydrogen burner (1-3) is connected with high-temperature pyrolysis reactor (1-1), it is characterized in that, described Pintsch process reaction unit (1-1) comprises high-temperature pyrolysis reactor (2-1), and described high-temperature pyrolysis reactor (2-1) comprises the mixing tank (2-1a) and reactor (2-1b) that connect up and down;
Described mixing tank (2-1a) and reactor (2-1b) be internally connected with removable thermopair (2-13) moving up and down; Described reactor (2-1) internal-response district is connected with quenching apparatus moving up and down (2-11a);
The two side that described mixing tank (2-1a) is relative is tangentially respectively arranged with superheated vapour entrance (3-1) and gas-liquid mixed material entrance (3-3), and described mixing tank (2-1a) top is in axial direction provided with Gaseous materials entrance (3-2); Wherein said superheated vapour entrance (3-1) is connected with oxy-hydrogen burner (1-3).
2. device according to claim 1, is characterized in that, described device also comprises the gentle pyrolyzer (1-5) of polyolefine and is connected with high-temperature pyrolysis reactor (1-1).
3. device according to claim 1 and 2, is characterized in that, described device also comprises preheating gasification installation (1-4), is arranged between high-temperature pyrolysis reactor (1-1) and the gentle pyrolyzer (1-5) of polyolefine.
4. device according to claim 2, it is characterized in that, Gaseous materials entrance (3-2) and the gas-liquid mixed material entrance (3-3) of described mixing tank (2-1a) are connected to raw material preheating gasification installation (1-4).
5. the device according to claim 1,2 or 3, is characterized in that, described oxy-hydrogen burner (1-3) is connected with decoking regeneration reactor (1-2).
6. a method for oxyhydrogen combustion method direct heating cracking waste polyolefin, comprises the following steps:
1) waste polyolefin is carried out gentle cracking and obtain liquid hydrocarbon, using liquid hydrocarbon as cracking stock;
2) hydrogen and oxygen delivery are entered oxy-hydrogen burner, burning generates superheated vapour, makes the temperature range of superheated vapour be 800 ~ 2000 DEG C;
3) superheated vapour and cracking stock are delivered into Pintsch process reaction unit respectively, superheated vapour and cracking stock are mixed to form rapidly scission reaction material in the mixing zone of high-temperature pyrolysis reactor, and make scission reaction material be warming up to scission reaction temperature 750 ~ 1000 DEG C instantaneously; Wherein, above-mentioned cracking stock and superheated vapour hybrid mode in mixing zone is: water vapor tangentially enters the mixing zone of Pintsch process reaction unit, and the mixing zone that cracking stock enters Pintsch process reaction unit vertically or tangentially mixes with high-temperature water vapor;
4) there is scission reaction in scission reaction material in the mixing zone and reaction zone of high-temperature pyrolysis reactor, generates split product;
5) by quenching system, the temperature of split product is down to less than 500 DEG C, thus stops the carrying out of scission reaction.
7. the method for cracking waste polyolefin according to claim 6, is characterized in that, described step 3) cracking stock is first delivered into preheating gasifying device, in preheating gasifying device, temperature is 200 ~ 600 DEG C, obtains the cracking stock after preheating; Cracking stock after superheated vapour and preheating is delivered into Pintsch process reaction unit respectively.
8. the method for cracking waste polyolefin according to claim 6, is characterized in that, all changes Gaseous materials or gas-liquid mixed material after described cracking stock preheating into.
9., according to the method for the arbitrary described cracking waste polyolefin of claim 6-8, it is characterized in that, described step 1) between hydrogen and oxygen mass ratio be 1:5 ~ 1:8.
10., according to the method for the arbitrary described cracking waste polyolefin of claim 6-8, it is characterized in that, described step 2) in the mass ratio of water vapor and cracking stock can be 20:1 ~ 4:1.
11., according to the method for the arbitrary described cracking waste polyolefin of claim 6-8, is characterized in that, described step 3) the scission reaction residence time is 0.01 ~ 0.2s.
12., according to the method for the arbitrary described cracking waste polyolefin of claim 6-8, is characterized in that, described waste polyolefin comprises polyethylene or polypropylene or the mixture of the two.
The method of 13. cracking waste polyolefins according to claim 6-8, is characterized in that, described step 1) with the water at low temperature steam that water or scission reaction process reclaim, temperature adjustment is carried out to superheated vapour.
The method of 14. cracking waste polyolefins according to claim 6-8, is characterized in that, step 4) gained split product enters separation system after cooling and Waste Heat Recovery System (WHRS) are cooled to room temperature.
The method of 15. cracking waste polyolefins according to claim 6-8, it is characterized in that, described high-temperature pyrolysis reactor inwall forms coking, and the connection of Pintsch process reaction unit and oxy-hydrogen burner switches to the connection of decoking regeneration reactor and oxy-hydrogen burner, enters decoking reproducer; Described superheated vapour delivers into decoking regeneration reactor, and the temperature of adjustment superheated vapour, makes de-coking operations temperature control at 900 ~ 1100 DEG C, produces gas.
The method of 16. cracking waste polyolefins according to claim 15, is characterized in that, the air temperature ranges that decoking reproducer generates is 200 ~ 400 DEG C.
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| CN106520176A (en) * | 2016-11-21 | 2017-03-22 | 中国科学院过程工程研究所 | Method for using polyolefin plastic to prepare micromolecule alkene |
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