CN116286073A - Method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on concentrating solar heat source - Google Patents
Method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on concentrating solar heat source Download PDFInfo
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- CN116286073A CN116286073A CN202211586990.2A CN202211586990A CN116286073A CN 116286073 A CN116286073 A CN 116286073A CN 202211586990 A CN202211586990 A CN 202211586990A CN 116286073 A CN116286073 A CN 116286073A
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 70
- 239000010920 waste tyre Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 67
- 239000010985 leather Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000011973 solid acid Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 13
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 10
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 230000010485 coping Effects 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000010000 carbonizing Methods 0.000 description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- 238000004451 qualitative analysis Methods 0.000 description 10
- 238000004445 quantitative analysis Methods 0.000 description 10
- 230000000630 rising effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/80—Rubber waste, e.g. scrap tyres
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on a concentrated solar heat source, which is a novel synergistic and efficient conversion mode of organic residues of scraped cars under a heat source, constructs an organic solid waste self-catalytic system, selects different coping methods according to the element constitution and physical and chemical characteristics of the organic residues of the scraped cars, prepares waste sponge and leather with rich functional groups and high content of hetero elements into biochar, obtains carbon-based solid acid after acid treatment, catalyzes pyrolysis of waste tire particles by adopting a concentrated solar simulated light source as a reaction heat source, improves yield and quality of pyrolysis oil, and provides a brand-new, harmless and resource way for recycling the organic residues of the scraped cars.
Description
Technical field:
the invention relates to the technical field of waste treatment, in particular to a method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on a concentrated solar heat source.
The background technology is as follows:
at present, people focus on the recycling of the scraped car mainly on the inorganic metal component part of the scraped car, however, the organic residue part (such as waste tires, waste sponge, waste leather and the like) of the scraped car also has considerable recyclable total amount, so the efficient cleaning, recycling and upgrading of the organic residue of the scraped car are also worth focusing on. Waste tires, waste sponge and waste leather are the three most representative organic vehicle residues. The content of the waste tire C is up to more than 80%, and the improper disposal mode can cause great waste of resources and emission of a large amount of greenhouse gases. In contrast, waste sponge and waste leather have a high oxygen content, and it is difficult to obtain high quality pyrolysis oil having a low oxygen content by pyrolysis alone. In addition, the waste leather and the waste sponge also contain a lot of impurity elements such as N, S, so the waste leather and the waste sponge are not suitable for recycling in a pyrolysis mode from the aspect of recycling resources.
The energy sources of the traditional pyrolysis means are mainly electric heating or fuel combustion heat release, and the method has high energy consumption and is accompanied with pollutant emission.
The invention comprises the following steps:
the invention aims to provide a method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on a concentrated solar heat source, which selects different coping methods according to the constitution and physical and chemical characteristics of organic residues of scraped cars, prepares waste sponge and leather with rich functional groups and high content of hetero elements into biochar, obtains carbon-based solid acid after acid treatment, catalyzes pyrolysis of waste tire particles by adopting a concentrated solar simulated light source as a reaction heat source, constructs an organic solid waste self-catalytic system, improves yield and quality of pyrolysis oil, and provides a brand-new harmless and recycling way for recycling the organic residues of the scraped cars.
The invention is realized by the following technical scheme:
a method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on concentrated solar heat sources comprises the following steps:
(1) Placing waste sponge or leather particles of the organic scrap of the scraped car in a quartz boat, feeding the waste sponge or leather particles into a tube furnace, heating to 400-800 ℃ at a heating rate of 10 ℃/min under inert atmosphere, preserving heat for 1-12 h for carbonization, taking out and grinding after the reaction is naturally cooled, then placing the waste sponge or leather particles in 1-12 wt.% hydrofluoric acid (preferably 9-10 wt.%, most preferably 10 wt.%) for stirring for 4-8h at room temperature to remove inorganic components, washing and filtering until filtrate is neutral, and taking out and grinding after vacuum drying at 75-85 ℃ for 10-12h to obtain biochar;
(2) The biochar prepared in the step (1) is loaded with phosphate groups, and the specific steps are as follows: adding biochar into deionized water, adding phosphoric acid, mixing, performing ultrasonic dispersion for 12 hours, washing with deionized water, filtering, repeating for three times, placing a filter cake in a vacuum drying oven, vacuum drying at 75-80 ℃ for 12-14 hours, cooling, taking out, and grinding to obtain carbon-based solid acid loaded by phosphate groups;
or loading the biochar prepared in the step (1) with sulfonic acid groups, wherein the specific steps are as follows: adding biochar into dichloromethane, adding chlorosulfonic acid, stirring at room temperature to 70 ℃ (preferably 60 to 70 ℃ and most preferably 65 ℃) for reaction for 12 hours, washing with deionized water, filtering, repeating for three times, placing a filter cake into a vacuum drying box, vacuum drying at 75 to 80 ℃ for 12 to 14 hours, cooling, taking out and grinding to obtain carbon-based solid acid loaded by sulfonic acid groups;
(3) Placing the carbon-based solid acid catalyst loaded by the phosphoric acid group or the carbon-based solid acid catalyst loaded by the sulfonic acid group prepared in the step (2) and the waste tire particles of the organic waste tire of the scraped car into a reactionIn the kettle, adjusting the power of a concentrating solar simulated light source, heating reactants with different fluence densities in an inert atmosphere, discharging pyrolysis products through purge gas, and collecting liquid-phase products after condensation; the mass ratio of the waste tires to the carbon-based solid acid catalyst is 1:0.5 to 5; the illumination energy flow density of the concentrated solar pyrolysis is 500-1500 KW/m 2 The pyrolysis temperature is 400-900 ℃, and the pyrolysis time is 0.5-3 h.
Preferably, the mass-to-volume ratio of the biochar to the phosphoric acid or chlorosulfonic acid in the step (2) is 1g: (0.1-2) mL.
Preferably, the particle size of the scrap tire particles is 50 to 200 mesh.
The beneficial effects of the invention are as follows:
1) The invention uses the abundant functional groups of the waste leather and the waste sponge, and the carbonized carbon-based solid acid prepared by carbonizing the waste leather and the waste sponge is used as a catalyst for pyrolysis of the waste tire, so that the catalytic activity can be improved by virtue of acid-base sites provided by the abundant functional groups while reducing carbon emission. Under the catalysis of the carbon-based solid acid, the waste tires can be converted into high-quality pyrolysis oil, so that the recycling rate of resources is improved from an economic perspective. The carbon-based solid acid raw material is common and easy to regenerate, is a low-cost catalyst, and has good economic benefit.
2) The invention uses the concentrated solar energy with high energy density to heat the reactant, so that the consumption of traditional fossil energy can be reduced, and no extra pollutant is introduced in the whole pyrolysis process. In addition, the light source supplies heat, and besides the heat required by the reaction, the light source can excite the photocatalytic activity of part of the catalyst, so that the catalytic effect is improved, high-yield high-quality pyrolysis oil is obtained, and the method has wide research prospect and practical application value.
3) The invention provides a method for preparing high-quality pyrolysis oil by catalytic pyrolysis of waste tires based on a concentrated solar heat source, which utilizes a simulated solar light source to supply heat to the waste tires in an anaerobic environment, and realizes high-efficiency conversion from the waste tires to the high-quality pyrolysis oil by regulating pyrolysis parameters under the catalysis of waste sponge/waste leather derived carbon-based solid acid, thereby providing a new mode for pyrolysis of organic residues of scraped automobiles and expanding the application fields of waste sponge and waste leather.
In a word, the invention explores a novel synergistic and efficient conversion mode of the organic residues of the scraped car under the heat source, constructs an organic solid waste self-catalytic system, selects different coping methods according to the element constitution and physical and chemical characteristics of the organic residues of the scraped car, prepares the waste sponge and leather with rich functional groups and high content of the hetero elements into biochar, obtains carbon-based solid acid after acid treatment, adopts a concentrated solar simulated light source as a reaction heat source, catalyzes pyrolysis of waste tire particles, improves the yield and quality of pyrolysis oil, and provides a brand-new harmless and recycling way for recycling the organic residues of the scraped car.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of deionized water with 1mL of phosphoric acid (H 3 PO 4 AR,85 wt.%) for 12h, followed by washing, filtration, repeating three times, vacuum drying the filter cake at 80 ℃ for 12h, cooling, grinding to obtain carbon-based solid acid catalyst, designated 1P-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the carbon-based solid acid catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 2 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 62.1wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 87.9wt.%, as shown in table 1.
Comparative example 1:
the same as in example 1, except that no carbon-based solid acid catalyst was added during pyrolysis, the final pyrolysis oil yield was 40.7wt.%, and the pyrolysis oil aromatic content was 68.6wt.%.
As can be seen from example 1 and comparative example 1, the carbon-based solid acid catalyst can significantly improve the yield and quality of the waste tire pyrolysis oil under the condition of concentrating solar heat supply.
Example 2:
(1) Placing the waste sponge of the scraped car organic residue in a quartz boat and sending the waste sponge into a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under inert atmosphere, carbonizing for 6 hours, taking out and grinding after the reaction is finished and naturally cooling, then removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering until filtrate is neutral, and taking out and grinding a filter cake after vacuum drying for 12 hours at 80 ℃ to obtain the biochar. To 1g of biochar was added 20mL of deionized water with 1mL of phosphoric acid (H 3 PO 4 AR,85 wt.%) for 12 hours, followed by washing, filtration, and drying to obtain carbon-based solid acid catalyst 1P-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 2 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 56.4wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain 77.3wt.% of aromatic hydrocarbon content in the pyrolysis oil, as shown in table 1 in detail.
Example 3:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar were added 20mL of methylene chloride and 1mL of chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 deg.C for reaction for 12 hr, washing and passingFiltering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 2 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 78.5wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain 93.2wt.% of aromatic hydrocarbon content in the pyrolysis oil, as shown in table 1 in detail.
Example 4:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 12 hours at 800 ℃ at a heating rate of 10 ℃/min under an inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 2mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 2S-LC12-800.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:5 are evenly mixed and then are put into a reaction kettle, and the ratio of the mixture to the water is 1500KW/m 2 Is heated to 900 c and held for 3 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 76.6wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 90.1wt.%, as shown in table 1.
Example 5:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing for 1 hour at 400 ℃ at a heating rate of 10 ℃/min under an inert atmosphere, taking out and grinding after the reaction is naturally cooled, then removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering until filtrate is neutral, taking out and grinding a filter cake after vacuum drying for 12 hours at 80 ℃ to obtain a raw materialAnd (5) charcoal. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) with 0.5mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 0.5S-LC1-400.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:0.5 is evenly mixed and then is placed in a reaction kettle, and 1000KW/m 2 Is heated to 400 c and held for 2 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 8.6wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 10.2wt.%, as shown in table 1.
Example 6:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 1mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed into a reaction kettle, and 800KW/m is used 2 Is heated to 700 c and maintained for 0.5h. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 63.6wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 80.9wt.%, as shown in table 1.
Example 7:
(1) Placing the waste leather of the scraped car organic residue into a quartz boat and sending into a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under inert atmosphere, carbonizing for 6 hours,and taking out and grinding after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing, filtering to neutrality, and taking out and grinding after the filter cake is dried in vacuum at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 1mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 50 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 1h. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 67.5wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain an aromatic hydrocarbon content of 82.2wt.%, as shown in table 1.
Example 8:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 1mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 3 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 72.0wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain 83.7wt.% of aromatic hydrocarbon content in the pyrolysis oil, as shown in table 1 in detail.
Example 9:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 1mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 150 mesh automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 800 c and maintained for 0.5h. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 73.6wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 85.0wt.%, as shown in table 1.
Example 10:
(1) Placing the waste leather of the scraped car organic residue in a quartz boat and sending the waste leather into a tube furnace, carbonizing the waste leather for 6 hours at the temperature rising rate of 10 ℃/min to 700 ℃ under inert atmosphere, taking out and grinding the waste leather after the reaction is naturally cooled, removing inorganic components by using 10wt.% hydrofluoric acid solution, washing and filtering the waste leather until filtrate is neutral, and taking out and grinding the filter cake after vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the biochar. To 1g of biochar was added 20mL of dichloromethane (CH 2 Cl 2 AR, 99.5%) and 1mL chlorosulfonic acid (ClHSO) 3 AR, 99%), stirring at 65 ℃ for reaction for 12 hours, washing, filtering and drying to obtain the carbon-based solid acid catalyst 1S-LC6-700.
(2) Mixing 200 meshes of automobile waste tire particles with the catalyst prepared in the step (1) according to the mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 2 hours. Sieving and recovering the carbon-based solid acid catalyst after the reaction is finished, and adopting the acidification step in (1)And regenerating the catalyst to obtain the regenerated carbon-based solid acid catalyst. Mixing 200 meshes of automobile waste tire particles with a regenerated carbon-based solid acid catalyst according to a mass ratio of 1:2 are evenly mixed and then are placed in a reaction kettle, 1300KW/m 2 Is heated to 700 c and held for 2 hours. After the reaction was completed, the pyrolysis oil obtained by condensation was collected, the yield of the pyrolysis oil was calculated to be 74.3wt.%, based on mass, and the pyrolysis oil was sent to GC-MS for qualitative and quantitative analysis to obtain the aromatic hydrocarbon content of 92.1wt.%, as shown in table 1. In comparison with example 1, it is clear that the catalysts mentioned in the present invention can recover good catalytic activity by regeneration.
TABLE 1
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (6)
1. The method for preparing the high-quality pyrolysis oil by catalytic pyrolysis of the waste tires based on the concentrated solar heat source is characterized by comprising the following steps of:
(1) Placing waste sponge or leather particles of the organic scrap of the scraped car into a quartz boat and sending into a tube furnace, heating to 400-800 ℃ at a heating rate of 10 ℃/min under inert atmosphere, preserving heat for 1-12 h for carbonization, taking out and grinding after the reaction is naturally cooled, then placing into 1-12 wt.% hydrofluoric acid, stirring at room temperature for 4-8h to remove inorganic components, washing and filtering until filtrate is neutral, drying, and taking out and grinding to obtain biochar;
(2) The biochar prepared in the step (1) is loaded with phosphate groups, and the specific steps are as follows: adding biochar into deionized water, adding phosphoric acid, mixing, performing ultrasonic dispersion for 12 hours, washing with deionized water, filtering, repeating for three times, drying a filter cake, taking out, and grinding to obtain carbon-based solid acid loaded by a phosphoric acid group;
or loading the biochar prepared in the step (1) with sulfonic acid groups, wherein the specific steps are as follows: adding biochar into dichloromethane, adding chlorosulfonic acid, stirring at room temperature to 70 ℃ for reaction for 12 hours, washing with deionized water, filtering, repeating for three times, drying a filter cake, taking out and grinding to obtain carbon-based solid acid loaded by sulfonic acid groups;
(3) Placing the carbon-based solid acid catalyst loaded by the phosphoric acid group or the carbon-based solid acid catalyst loaded by the sulfonic acid group prepared in the step (2) and the waste tire particles of the scrapped car organic residues in a reaction kettle, adjusting the power of a concentrating solar simulated light source, heating reactants with different fluence densities in an inert atmosphere, discharging pyrolysis products through purge gas, and collecting liquid-phase products after condensation; the mass ratio of the waste tires to the carbon-based solid acid catalyst is 1:0.5 to 5; the illumination energy flow density of the concentrated solar pyrolysis is 500-1500 KW/m 2 The pyrolysis temperature is 400-900 ℃, and the pyrolysis time is 0.5-3 h.
2. The method according to claim 1, wherein the mass to volume ratio of the biochar to the phosphoric acid or chlorosulfonic acid in the step (2) is 1g: (0.1-2) mL.
3. The method of claim 1, wherein the scrap tire particles have a particle size of 50 to 200 mesh.
4. The method of claim 1, wherein the drying of steps (1) and (2) is performed in a vacuum oven at 75-85 ℃.
5. The method of claim 1, wherein the hydrofluoric acid concentration of step (1) is 9 to 10wt.%.
6. The method of claim 1, wherein step (2) is: the biological carbon prepared in the step (1) is loaded with sulfonic acid groups, and the specific steps are as follows: adding biochar into dichloromethane, adding chlorosulfonic acid, stirring at 60-70 ℃ for reaction for 12 hours, washing with deionized water, filtering, repeating for three times, drying a filter cake, taking out and grinding to obtain the carbon-based solid acid loaded by sulfonic acid groups.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160151766A1 (en) * | 2013-07-12 | 2016-06-02 | National Institute Of Advanced Industrial Science And Technology | Carbon-containing solid acid having sulfonate group |
| CN113293023A (en) * | 2021-06-24 | 2021-08-24 | 南京林业大学 | Method for preparing high-quality oil from waste tires |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
| CN114921258A (en) * | 2022-05-17 | 2022-08-19 | 浙江大学 | Recyclable tire microwave in-situ catalytic pyrolysis method for preparing hydrogen-rich gas |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160151766A1 (en) * | 2013-07-12 | 2016-06-02 | National Institute Of Advanced Industrial Science And Technology | Carbon-containing solid acid having sulfonate group |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
| CN113293023A (en) * | 2021-06-24 | 2021-08-24 | 南京林业大学 | Method for preparing high-quality oil from waste tires |
| CN114921258A (en) * | 2022-05-17 | 2022-08-19 | 浙江大学 | Recyclable tire microwave in-situ catalytic pyrolysis method for preparing hydrogen-rich gas |
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