CN1699515A - Process for producing gasoline, diesel oil and active carbon by using waste rubbers - Google Patents
Process for producing gasoline, diesel oil and active carbon by using waste rubbers Download PDFInfo
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- CN1699515A CN1699515A CN 200410038241 CN200410038241A CN1699515A CN 1699515 A CN1699515 A CN 1699515A CN 200410038241 CN200410038241 CN 200410038241 CN 200410038241 A CN200410038241 A CN 200410038241A CN 1699515 A CN1699515 A CN 1699515A
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Abstract
The invention discloses a process for producing gasoline, diesel oil and active carbon by using waste rubber, wherein the process comprises using high temperature gas as the heating source, carrying heat transfer and equipment heating in a common heat-treating facility through the direct contact between the heating source with rubber waste or materials, carrying out decomposition reaction under low-temperature condition, reclaiming and utilizing gas phase hydrocarbons after decomposition, carrying out high temperature activation to the decomposed residual charcoal by using the high temperature gas as activating agent and heating source.
Description
TECHNICAL FIELD OF THE INVENTION
The present invention relates to handle the method for waste rubber, relate to particularly and in same equipment, adopt two kinds of different temperature and direct heat transfer mode, handle waste rubber to produce gasoline, diesel and process of active carbon by thermo-cracking and catalytic pyrolysis.
Technical background
About being raw material production gasoline, diesel and process of active carbon with the waste rubber, have a lot of reports; The inventor is at CN 1066482 C, EP-0863197, Japan's special permission the 3043429th and USP5,744, in 668, disclose waste rubber and all be in the pyrolytic reaction still with reactor outside thermal source carry out indirect heating and carry out scission reaction, and the hydrocarbon ils and the carbon black that produce behind the rubber cracking are recycled; The defective of indirect heating maximum is exactly that thermo-efficiency is low with the utilization ratio of heat, the energy consumption height, and the speed of heat scission reaction is slow, and the cracking time is long, and yielding poorly of the Equipment for Heating Processing of unit volume causes production cost to rise; Directly heating causes the metal material distortion of reactor easily and damages shortened equipment life to reactor; Especially, alkali absorption unit behind the heat scission reaction or fusion mineral alkali are to remove in the cracked gas the deleterious acidity of catalyzer and other gas with foreign flavor by the chemical process of acid-base neutralisation; But can not eliminate harm and the poisoning of neutral organic polymer viscosity tar that cracked gas contains to catalyzer in the fixed bed of postposition; Neutral polymer viscosity tar not with mineral alkali generation chemical reaction;
In CN1373085A, reported with the carbon black that produces after the waste rubber cracking as the raw material production process of active carbon, be that the carbon black that will reclaim is ground into Powdered earlier and metal is removed in magnetic separation, carry out further carbonization and activation treatment with fluidized-bed process and high-temperature water vapor again, make it become gac; This method technical process is long, plurality of devices operation, and complex structure, steam energy consumption height; Waste rubber or raw material must in turn carry out the processing more than at least two steps respectively in multiple devices such as thermal cracker and another charing and activatory fluidized-bed: promptly, the first step, earlier waste rubber is placed in the apparatus for thermal cleavage, thermo-cracking under hot conditions more than 400 ℃ makes it be transformed into carbon black, the carbon black that collection and low temperature deposit are discharged by apparatus for thermal cleavage; In second step,, make it become gac with the carbon black of low temperature deposit activation treatment through high-temperature water vapor heating carrying out further charing and fluidized-bed process; Pulverize after the high temperature carbon black that the first step produces need be reduced to low temperature, the heat that causes comprising in the carbon black loses in a large number; The powdered carbon under low temperature or the normal temperature is elevated to 800-900 ℃ of activation treatment of carrying out for second step again, need absorbs a large amount of heats again, this two step or multistep processes have caused a large amount of losses and the additive decrementation of heat, and energy consumption cost is raise; The main inventive point of this method is exactly the activating process that adopts fluidized-bed, makes water vapor and solid powdered carbon uniform contact fully; Yet fluidized-bed is big or small to the particle (or diameter) of raw material, the requirements such as proportion, viscosity and water content of raw material are all very high, and is wayward in the production; Make powdered carbon in the activator with water vapor, its humidity is very high, easily produces laying dust and line clogging in the circulation of fluidized-bed; The fluidized-bed structure complexity, fluidic pressure and flow easily change, and cause the 800-900 ℃ of difficult control of the operation under the high temperature; Particularly the powdered carbon under 800-900 ℃ of condition of high temperature is very trickle, and its seepage force is very strong, is easy to the tail gas of discharging, and together goes here and there the filter cloth of cyclonic separator back, is distributed to the pollution that causes in the atmospheric environment environment;
Of the present invention open
The invention provides with waste rubber and produce gasoline, diesel and process of active carbon, more particularly, the present invention relates to adopt high-temperature gas as thermal source, in same Equipment for Heating Processing, thermal source directly contacts with waste rubber or material and takes place to conduct heat and heat to equipment, carry out the scission reaction under the cold condition earlier, and reclaim and utilize gas phase hydrocarbon after the cracking, as activator and thermal source residue carbon of biomass pyrolysis is carried out high-temperature activation with high-temperature gas then and obtain process of active carbon;
May further comprise the steps by method of the present invention:
Bi. in the Equipment for Heating Processing of described waste rubber being packed into and airtight this equipment;
Ii. high-temperature flue gas is passed in this Equipment for Heating Processing as thermal source, and directly contacts,, kept 0.2-8 hour, carry out heat scission reaction, the gaseous substance of collecting and utilizing Equipment for Heating Processing to discharge at 350-600 ℃ to the equipment heating with material;
Iii. use high-temperature flue gas and/or superheated vapour as thermal source and activator, Gu solid carbon residue last after the thermo-cracking in this Equipment for Heating Processing is carried out gas---two-phase is contact or activation treatment directly, temperature in the activation in the Equipment for Heating Processing is controlled at 600-1200 ℃, the activation terminal point is determined by sample examination, and is collected, purifies and handle the tail gas of discharging in the activation according to a conventional method;
Iv. the carbon residue after activation being finished is discharged from Equipment for Heating Processing, and collects according to a conventional method and processing obtains active carbon finished products;
The present invention has selected unique catalyzer for use, and before catalytic pyrolysis, added and sloughed tar and the physical adsorption device of the deleterious material of catalyzer (as sour gas), guaranteed that the interior solid catalyst of fixed bed does not stop up, the pollution of the objectionable impuritiess such as viscosity tar of not poisoned, be not subjected to, prolong the work-ing life of catalyzer, guaranteed the stable of oil quality and production; The noncondensing inflammable gas that scission reaction produces can turn back to burning generation high-temperature flue gas recovery heat in the roasting kiln; Produce water vapor with fume afterheat; Thermo-efficiency height of the present invention, technical process are lacked, equipment is simple and long service life, have overcome the problem that prior art exists.
Main chemical cracking reaction of the present invention is as follows:
N[C+H
2+ C
2H
2+ C
2H
6+ C
3H
8+ C
3H
6+ C
4H
8+ C
4H
10+ C
5H
10+ C
5H
12+ C
6H
6+ C
7H
8+ ... C
12H
24+ C
12H
26+ ... + C
20H
40+ C
20H
42+ ... + C
25H
52], wherein, C
6H
14-C
12H
24Be gasoline component, C
12H
26-C
20H
42Be diesel component, and CH
4-C
4H
10Be inflammable gas;
Brief description of drawings
Fig. 1 is a reacting flow chart of the present invention.
In accompanying drawing 1,1-waste rubber raw material, 2-charge cavity valve, the 3-Equipment for Heating Processing, 4-gac discharge hole valve, 5-roasting kiln, the 6-adsorption unit, 7-fixed bed, 8-condenser, the 9-oil-gas separator, 10-purification pot, 11-heat exchange still, the 12-separation column, 13-stripping tower, 14-gas storage holder, the 15-water-sealed tank, 16-gasoline condenser, 17-diesel oil condenser, 18-gasoline water-and-oil separator, 19-diesel oil water-and-oil separator, 20-gasoline tank, 21-diesel oil tank, the 22-oil pump, the active carbon residue of 23-, 24-waste heat boiler, 25-induced draft fan; The 26-vacuum fan, the 27-scavenging tower; 28-venting hole valve;
Detailed description of the present invention
According to the present invention, will give up natural rubber and/or useless synthetic rubber (NR, SR, SBR, BR, IR, CR, NBR, EPM and IIR) anticipate, remove impurity; To handle well The scrap rubber raw material join the Equipment for Heating Processing 3 from charging aperture valve 2; Give combustion furnace 5 drums Enter air and turn back to combustion with the noncondensing imflammable gas that provides thermal source or cracking reaction is produced Burn in the stove 5 and burn, burning produces the anaerobic high-temperature flue gas; High-temperature flue gas is directly passed into heat In the treatment facility 3, allow high-temperature flue gas contact with the scrap rubber raw material, heat exchange takes place give scrap rubber Heating; Heat scission reaction pressure is normal pressure or a little higher than normal pressure or 0.02-0.1Mpa, and temperature is 350-600 ℃; In this temperature, pressure scope, after the scrap rubber raw material in the Equipment for Heating Processing is heated Heat scission reaction takes place, and resolves into solid carbon residue and micromolecular hydro carbons in Equipment for Heating Processing 3 Gaseous substance; With the hydro carbons gaseous substance of thermal cracking generation and the mixture gas of low-temperature flue gas formation Body is together discharged from the top of Equipment for Heating Processing 3, introduces bulk or granular active carbon are housed Adsorbent equipment 6 carries out physical absorption and filtration, with charcoal absorption with remove the hydro carbons gaseous substance In organic polymer viscosity tar and flue gas in the acidic materials harmful to catalyst that contain, The macromolecule viscosity tar material that produces in the elimination thermal cracking is to the catalyst in the fixed bed and pipe The obstruction of road equipment, remove smoke and rubber cracking after in contained acidic materials to catalyst Adverse effect; The gaseous substance that ejects through absorbent charcoal adsorber 6 carries out through fixed bed 7 again The catalytic cracking of hydro carbons gaseous substance, and carry out the reaction such as a series of isomerization, generate gasoline, The compounding substances such as diesel component and other imflammable gas such as gas use in the fixed bed 7 Catalyst can select the inventor disclosed XL and/or DL in CN1066482C to urge Change agent; The catalytic reaction temperature is 200-400 ℃ in the fixed bed, and pressure is 0.02-0.1Mpa, Air speed is 1-2000/h;
Follow flue gas together to enter condenser 8 condensations by the crackate that catalytic fixed bed 7 is drawn To room temperature, and enter oil gas in device 9, in gs-oil separator 9, gas and liquid are divided Leave, the liquid that is condensed is the mixture of gasoline, diesel, and this mixture is from gs-oil separator 9 Be input to purification pot 10; Mixing material oil in the purification pot 10 through inorganic acid (such as sulfuric acid, phosphorus Acid ...) alkali (such as NaOH, KOH) process and removing foreign matter after, will locate with oil pump 22 Mixing material oil pump after the reason enters heat exchange kettle 11, and be heated to 250-350 ℃ and enter fractionating column 12, Do not coexist according to gasoline, diesel oil boiling range and to separate in the fractionating column 12, gasoline enters condenser from cat head 16, enter gasoline tank 20 through oil water separator 18; Diesel oil enters vapour from fractionating column 12 middle parts Stripper 13, after the superheated steam effect, diesel oil enters condenser 17, through oil water separator 19, Enter at last diesel oil tank 21; The little molecule combustibility of in gs-oil separator 9, not condensed Gas or gas follow flue gas together to be incorporated into by air-introduced machine 25 from the top of oily device separator 9 Deposit or buffering in the gas storage holder 14; Be subjected to the graviational interaction of air-introduced machine 25, contain imflammable gas Mist from gas storage holder 14, after water sealed tank 15 is processed, be returned to combustion furnace 5 In burn as thermal source, burning produces high-temperature flue gas and heat, and gives with this high-temperature flue gas Equipment for Heating Processing and cracking reaction heat supply; The high-temperature flue gas that produces in the combustion furnace 5 has multiple whereabouts With purposes, one, flowed in the Equipment for Heating Processing 3 by the draft effect of air-introduced machine 25, give heat Rubber raw materials heating in the treatment facility 3 or supply cracking reaction institute calorific requirement; Its two, can lead to Cross air exhauster 26 and be incorporated into other firing equipment and carry out heat supply or heat transfer, as sending out to superheated steam Give birth to device, waste heat boiler 24 or boiler, heat exchange kettle 11 ... etc. the equipment heat supply; Heat supply or Flue-gas temperature after the heat transfer is lowered, through gas cleaning process up to standard after discharger or emptying; In the activation process, be blown into the flow of combustion air of combustion furnace 5 and air exhauster 26 through chimney Outwards emptying flue gas flow is consistent;
When the scrap rubber cracking in the Equipment for Heating Processing 3 volatilization of complete or gaseous substance complete after, continue And Equipment for Heating Processing 3 interior remaining cracked residues or solid carbon residue are carried out activation process, make it Be transformed into active carbon; The present invention adopts high-temperature gas as activator, such as high-temperature flue gas or overheated Water vapour or with the high-temperature gases such as mist of high-temperature flue gas and superheated vapour; Begin activation The time, high-temperature gas is passed in the Equipment for Heating Processing 3, the temperature in the Equipment for Heating Processing 3 is carried High to 600-1200 ℃, pressure is 0.02-0.1Mpa; Allow after high-temperature gas and the cracking reaction surplus Gu surplus solid carbon residue carries out gas---the direct contact of two-phase activates the place to the solid carbon residue Reason; During activation process, close the steam vent valve of the hydro carbons gaseous substance at Equipment for Heating Processing 3 tops 28, open connecting pipeline and valve between Equipment for Heating Processing 3 and the gas purification tower 27, will Waste gas after the activation or tail gas are incorporated into from Equipment for Heating Processing 3 and carry out the feature of environmental protection the purifying column 27 Purified treatment, waste gas or tail gas are processed qualified rear discharger or emptying in purifying column 27; In the activation, the reaction of water vapour and charcoal is the endothermic reaction, and water vapour can reduce activation temperature, Temperature in the end or the control activation process falls in quantity delivered that can be by water vapour or flow; Activation eventually Point is definite by sample examination, the methylenum careuleum decolorizing ability of common active carbon 〉=10 or iodine sorption value 〉=900 o'clock, it was qualified to be called chemical examination; By the activation of high-temperature gas, the carbon residue that cracking reaction produces Be transformed into active carbon residue 23; To meet chemically examine examination criteria active carbon residue 23 by discharging Ports valve door 4 is discharged Equipment for Heating Processing 3; Then to active carbon residue 23 according to routine or known Method is processed or is purified, namely carry out iron removal by magnetic separation, pickling, washing, dehydration, drying, Be ground into powder or granulation, packing, obtain at last Powdered or the granular active carbon finished product.
Below illustrate in greater detail the present invention by specific embodiment, but the present invention is not limited.
Embodiment
With 1000KG damaged tire flush away silt, be crushed to the 5-10 centimetre, join the Equipment for Heating Processing 3 from charge cavity valve 2; Blast air for roasting kiln 5 and fuel oil is provided and/or the noncondensing inflammable gas that scission reaction produces turned back in the roasting kiln 5 and burn, the high-temperature flue gas that burning is produced directly feeds in the Equipment for Heating Processing 3, allow high-temperature flue gas contact, and give Equipment for Heating Processing 3 and waste rubber heating with waste rubber; Temperature in the Equipment for Heating Processing 3 is controlled at 420-500 ℃, and reaction pressure is at 0.04-0.08Mpa; In this temperature, pressure scope, heat scission reaction took place after the waste rubber in the Equipment for Heating Processing 3 was heated, resolve into solid carbon residue and micromolecular hydro carbons gaseous substance; Micromolecular hydro carbons gaseous substance is followed the useless flue gas of low temperature together, side by side discharges from the top of Equipment for Heating Processing 3, enters the adsorption unit 6 that granular active carbon is housed then and adsorbs and filter; The gaseous substance that ejects behind absorbent charcoal adsorber 6 fixed bed through being mounted with the XL catalyzer 7 again carries out the catalytic cracking of hydro carbons gaseous substance, generate gasoline, diesel component and inflammable gas, the catalyzed reaction temperature is 290-380 ℃, and pressure is 0.04-0.08Mpa; Follow flue gas together to be condensed to room temperature by the crackate that catalytic fixed bed 7 is drawn through entering condenser 8, and enter oil gas in device 9, in oil-gas separator 9, gas and liquid are separated to be opened, by agglomerative liquid is the mixture of gasoline, diesel, and this mixture is input to purification pot 10 from oil-gas separator 9; Mixing liquid oil in the purification pot 10 is behind sulfuric acid and caustic soda processing and removing foreign matter, mixing liquid oil pump after will handling with oil pump 22 is gone into heat exchange still 11, is heated to 280-320 ℃ and enters separation column 12 and carry out fractionation, after fractionation and ordinary method are handled, obtain gasoline 101KG, diesel oil 280KG; Wherein, the RON of gasoline is 95.5, does≤205 ℃; Diesel-fuel cetane number is 46.8, zero pour≤-25 ℃;
After the volatilization of the gaseous substance cracking in the Equipment for Heating Processing 3 finishes, then cracked residue is carried out activation treatment; Adopt high-temperature flue gas and/or superheated vapour as thermal source and activator; When beginning to activate, 900-1300 ℃ of high-temperature flue gas or activator are passed in the Equipment for Heating Processing 3, the temperature in the reactivation process is controlled at 800-980 ℃, and pressure maintains 0.04-0.07Mpa; Gu allow the remaining carbon residue of high-temperature gas and cracking carry out gas---the direct of two-phase contacts and activation treatment; In the activation treatment, the useless tail gas after the activation is incorporated into the scavenging tower 27 from Equipment for Heating Processing 3, method for gas purification routinely carries out vent gas treatment, qualified back emptying up to standard; Use the feed rate reduction of water vapor or the activation temperature in the adjusting Equipment for Heating Processing 3 in the activation; Activate after 55 minutes, sample examination obtains following analytical results: the methylenum coeruleum decolorizing ability of gac is 11, iodine sorption value 910, and activation treatment is finished; To activate carbon residue 23 then and discharge Equipment for Heating Processing 3 by discharge hole valve 4, and activation carbon residue 23 is carried out further iron removal by magnetic separation, pickling, washing, dehydration, drying, pulverizing and packing according to the method for routine, obtain 350KG powdered active carbon finished product at last, wherein, the ignition residue of gac≤4%, the methylenum coeruleum decolorizing ability is 11, and PH is 5-7, loss on drying≤10%.
Industrial applicibility
According to the inventive method, with scrap rubber be raw material can produce the stable gasoline of productive rate, Diesel oil and active carbon have guaranteed that industrialization produces continuously.
Claims (2)
1, produce gasoline, diesel and process of active carbon with waste rubber, may further comprise the steps:
I. in the Equipment for Heating Processing of described waste rubber being packed into and airtight this equipment;
Ii. high-temperature flue gas is passed in this Equipment for Heating Processing as thermal source, and directly contacts,, kept 0.2-8 hour, carry out heat scission reaction, the gaseous substance of collecting and utilizing Equipment for Heating Processing to discharge at 350-600 ℃ to the equipment heating with material;
Iii. use high-temperature flue gas and/or superheated vapour as thermal source and activator, Gu solid carbon residue last after the thermo-cracking in this Equipment for Heating Processing is carried out gas---two-phase is contact or activation treatment directly, temperature in the activation in the Equipment for Heating Processing is controlled at 600-1200 ℃, feed rate with superheated vapour reduces and the adjusting activation temperature, the activation terminal point is determined by sample examination, and method for gas purification routinely activates the processing of tail gas, qualified back up to standard discharging;
Iv. the activation carbon residue after activation being finished is discharged from Equipment for Heating Processing, and collects according to a conventional method and processing obtains active carbon finished products;
2, press the method for claim 1, it is characterized in that, described collection and the gaseous substance that utilizes Equipment for Heating Processing to discharge are meant: the hydro carbons gaseous substance of thermo-cracking generation and the gas mixture of low-temperature flue gas formation are together discharged from Equipment for Heating Processing, being incorporated into the adsorption unit that granular active carbon is housed adsorbs and filters, again through catalytic cracking, condensation, after separation reaches and handles according to a conventional method, the hydro carbons gaseous substance is converted to gasoline and diesel oil, incoagulable inflammable gas and waste gas together turn back to the roasting kiln generation high-temperature flue gas that burns, and the heat and the high-temperature flue gas that utilize burning to release are given Equipment for Heating Processing and scission reaction heat supply;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100382411A CN1306010C (en) | 2004-05-18 | 2004-05-18 | Process for producing gasoline, diesel oil and active carbon by using waste rubbers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100382411A CN1306010C (en) | 2004-05-18 | 2004-05-18 | Process for producing gasoline, diesel oil and active carbon by using waste rubbers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1699515A true CN1699515A (en) | 2005-11-23 |
| CN1306010C CN1306010C (en) | 2007-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100382411A Expired - Fee Related CN1306010C (en) | 2004-05-18 | 2004-05-18 | Process for producing gasoline, diesel oil and active carbon by using waste rubbers |
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|---|---|
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| WO2008131643A1 (en) * | 2007-04-25 | 2008-11-06 | Huihong Chen | Method and apparatus for combined recycling of waste polymer material or joint production with carbon black |
| WO2011150588A1 (en) * | 2010-06-02 | 2011-12-08 | 华南再生资源（中山）有限公司 | Production equipment for comprehensively utilizing renewable energy resources of waste plastics, tires and waste engine oil |
| CN101402745B (en) * | 2007-04-25 | 2012-07-04 | 陈汇宏 | Method and apparatus for combination regeneration, or coproduction with hydrocarbon black of waste and old macromolecule material |
| CN102660313A (en) * | 2012-05-26 | 2012-09-12 | 商丘市金源机械设备有限公司 | Scrap tire oil refining process |
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| CN1117517A (en) * | 1994-08-24 | 1996-02-28 | 中国长江动力公司(集团) | Method and equipment for catalytic cracking waste rubber |
| CN1145395A (en) * | 1995-08-08 | 1997-03-19 | 周鼎力 | Method and appts. for prodn. gasoline, diesel oil and carbon black by utilizing wasted rubber |
| WO2001083368A1 (en) * | 2000-04-28 | 2001-11-08 | Bluecher Hasso Von | Method for producing spherical activated carbon |
| JP2002308613A (en) * | 2001-04-10 | 2002-10-23 | 健郎 ▲とう▼ | Method for producing activated carbon |
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| WO2008131643A1 (en) * | 2007-04-25 | 2008-11-06 | Huihong Chen | Method and apparatus for combined recycling of waste polymer material or joint production with carbon black |
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| CN110883050B (en) * | 2019-11-13 | 2023-08-25 | 蚌埠学院 | High-water-content household garbage rapid recycling cleaning treatment method and system |
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