CN116274248A - Method for catalytically pyrolyzing biomass into levoglucosan and levoglucosone by using waste sponge derived carbon-based solid acid - Google Patents
Method for catalytically pyrolyzing biomass into levoglucosan and levoglucosone by using waste sponge derived carbon-based solid acid Download PDFInfo
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- CN116274248A CN116274248A CN202310154175.7A CN202310154175A CN116274248A CN 116274248 A CN116274248 A CN 116274248A CN 202310154175 A CN202310154175 A CN 202310154175A CN 116274248 A CN116274248 A CN 116274248A
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- 239000002699 waste material Substances 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000011973 solid acid Substances 0.000 title claims abstract description 42
- 239000002028 Biomass Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 42
- 239000003575 carbonaceous material Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000001291 vacuum drying Methods 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 10
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 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 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 241000219000 Populus Species 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- 238000004445 quantitative analysis Methods 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 238000004451 qualitative analysis Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DCNMIDLYWOTSGK-ZLUOBGJFSA-N (3R,4S,5S)-3,4,5,6-tetrahydroxy-2-oxohexanal Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)C(=O)C=O DCNMIDLYWOTSGK-ZLUOBGJFSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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Abstract
The invention discloses a method for converting biomass into levoglucosan and levoglucosone by catalytic pyrolysis of waste sponge-derived carbon-based solid acid, which utilizes rich nitrogen-containing functional groups and porous structures of waste sponge to obtain a catalyst for biomass pyrolysis of waste sponge-derived carbon-based solid acid through carbonization, acid treatment and other processes, converts biomass into chemicals such as LG/LGO with high added value, and provides a new idea for comprehensive recycling of biomass.
Description
Technical field:
the invention relates to the technical field of waste treatment, in particular to a method for converting waste sponge-derived carbon-based solid acid catalytic pyrolysis biomass into levoglucosan and levoglucosone.
The background technology is as follows:
the rapid rise of the new energy automobile industry directly leads to the increase of the number of scraped automobiles year by year. In the comprehensive recycling of scraped cars, nonmetallic components have been a difficulty in recycling. Compared with other nonmetallic constructions, the waste seat has the largest volume ratio, and the filler is waste sponge. The waste sponge mainly comprises polyurethane and polystyrene, and when the waste sponge is directly burnt, a large amount of styrene and toxic gas containing cyano are released, and CO is accompanied 2 Typical greenhouse gas emission can cause serious threat to environmental ecology. Therefore, the method has important significance for cleaning and efficiently recycling the waste sponge.
Biomass is considered as a renewable carbon source which is expected to replace petroleum, and after a catalytic pyrolysis process, a lignocellulose biomass macromolecule long chain can be converted into various micromolecular products after a series of processes such as depolymerization, deoxidation, reduction, aromatization, reforming and the like, wherein, the Levoglucosan (LG) and the Levoglucosone (LGO) are the most representative monomer derivatives, and have extremely high added value of products.
The invention comprises the following steps:
the invention aims to provide a method for converting waste sponge-derived carbon-based solid acid catalytic pyrolysis biomass into levoglucosan and levoglucosone, which comprises the steps of passing nitrogen-containing waste sponge throughThe modified product is carbonized at too high temperature and acid treated to obtain the product with rich properties
The carbon-based solid acid catalyst with the acid site carries out catalytic pyrolysis on lignocellulose biomass raw materials, converts biomass into Levoglucosan (LG) and Levoglucosone (LGO) with high added value, realizes the synergistic coupling conversion of waste sponge and biomass, and provides a brand-new harmless and recycling conversion way for the comprehensive recycling of the scraped car organic residues and the agriculture and forestry waste biomass.
The invention is realized by the following technical scheme:
a method for converting waste sponge-derived carbon-based solid acid catalyzed pyrolysis biomass into levoglucosan and levoglucosone, the method comprising the steps of:
(1) Washing, drying and crushing waste sponge from a scrapped car seat, feeding the waste sponge into a tube furnace, heating to 450-850 ℃ at a heating rate of 10 ℃/min under inert atmosphere, preferably 550-650 ℃, preserving heat for 1-6 hours to carbonize the waste sponge, taking out and grinding the waste sponge after carbonization, adding excessive deionized water to fully stir and filter the waste sponge, repeating the steps for three times, collecting a filter cake, taking out the filter cake after vacuum drying at 80 ℃ for 12 hours, and grinding the filter cake again to obtain the waste sponge-derived porous carbon material;
(2) And (3) loading the phosphate groups on the porous carbon material prepared in the step (1) by adopting an ultrasonic impregnation method, wherein the specific steps are as follows: adding the waste sponge-derived porous carbon material into deionized water, adding phosphoric acid, stirring and mixing, performing ultrasonic dispersion, washing with deionized water, filtering, repeating for three times, placing a filter cake in a vacuum drying oven, vacuum drying at 80 ℃ for 12 hours, cooling, taking out and grinding, then feeding the filter cake into a tubular furnace, and activating at 500 ℃ for 2 hours under an inert atmosphere to remove insufficiently-combined phosphoric acid, so as to obtain a waste sponge-derived carbon-based solid acid loaded by a phosphoric acid group;
or, loading the porous carbon material prepared in the step (1) with sulfonic acid groups by adopting a hydrothermal impregnation method, wherein the specific steps are as follows: adding a waste sponge derived porous carbon material into dichloromethane, then adding sulfuric acid or chlorosulfonic acid, carrying out turnover reaction for 6 hours at 50-100 ℃ (most preferably 80 ℃) in a reaction kettle, washing with deionized water after the reaction is finished, filtering, repeating for three times until filtrate is neutral, then placing a filter cake in a vacuum drying box, carrying out vacuum drying at 80 ℃, cooling, taking out and grinding to obtain waste sponge derived carbon-based solid acid loaded by sulfonic acid groups;
(3) Mixing the acid-loaded waste sponge-derived carbon-based solid acid prepared in the step (2) with a biomass raw material, and then placing the mixture into a fine quartz tube for catalytic pyrolysis reaction, wherein the mass ratio of the biomass raw material to the waste sponge-derived carbon-based solid acid catalyst is 1:0.1 to 2, the temperature rising rate is 10 to 10 4 The pyrolysis temperature is 350-850 ℃, preferably 550-800 ℃, most preferably 750 ℃ and the pyrolysis heat preservation time is 10-60 s.
The mass ratio of the consumption of phosphoric acid or sulfuric acid or chlorosulfonic acid to the mass ratio of the waste sponge derived porous carbon material is 0.1-2.
Preferably, the biomass raw material in the step (3) is one of cellulose, cassava residue, bagasse and poplar powder with the mesh number of 50-200, and is named as CE/CA/SU/PO-x, and x represents the mesh number.
The beneficial effects of the invention are as follows:
1) The catalyst for biomass pyrolysis of the carbon-based solid acid derived from the waste sponge is obtained by utilizing the rich nitrogen-containing functional groups and the porous structure of the waste sponge through carbonization, acid treatment and other processes, the biomass can be converted into chemicals such as LG/LGO with high added value, and a new idea is provided for comprehensive recycling of the biomass;
2) The catalyst used in the invention is prepared from the sponge in the scrapped car seat, has wide raw material sources and low price, can avoid environmental pollution caused by direct combustion or landfill of waste sponge, and has the dual characteristics of economy, feasibility and environmental friendliness.
3) The catalytic pyrolysis method provided by the invention realizes the cooperative coupling conversion between the two wastes, and has shorter conversion time, thereby having higher conversion efficiency and providing theoretical reference for practical application.
In a word, the invention explores a high-efficiency conversion mode for preparing high-added value chemicals by catalytically pyrolyzing biomass by using a carbon-based solid acid catalyst derived from waste sponge, constructs two representative organic solid waste coupling conversion systems, prepares waste sponge with higher content of hetero elements and rich nitrogen-containing functional groups into a porous carbon material, further obtains carbon-based solid acid through acid treatment, efficiently converts biomass raw materials into LG and LGO under the condition of rapid catalytic pyrolysis, and provides a harmless and recycling way for comprehensive recycling of waste sponge components in scrapped automobile organic residues and waste agriculture and forestry biomass.
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) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 650 ℃ under an inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, adding excessive deionized water for washing, filtering for three times, and vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing and filtering with deionized water, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently bonded phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded with phosphate groups, which is marked as 1PC650-3.
(2) Mixing 200 mesh cellulose (CE-200 particles) with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave a yield of 3.2% for L-glucan (LG) and 28.6% for L-glucosone (LGO), as detailed 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 LG yield was 18.6% and the LGO yield was 0.2%.
Comparative example 2:
the same as in example 1, except that the porous carbon material not acid-treated was added during pyrolysis, the final LG yield was 19.2% and the LGO yield was 0.3%.
Comparative example 3:
the same as in example 1, except that the raw material of the porous carbon material was waste cotton cloth having a low nitrogen content, the final LG yield was 15.9% and the LGO yield was 9.8%.
It is known from example 1, comparative example 2 and comparative example 3 that the waste sponge-derived carbon-based solid acid catalyst can significantly promote the conversion of LG to LGO, thereby improving the yield of LGO, and the catalytic activity is attributed to the synergistic effect of the supported acid sites and the nitrogen-containing functional groups of the waste sponge itself.
Example 2:
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 650 ℃ under an inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. 1g of waste sponge-derived porous carbon material is added into 5mL of dichloromethane, then 1g of sulfuric acid (98%) is added, the reaction kettle is turned over at 80 ℃ for 6h, deionized water is used for washing and filtering after the reaction is finished, the reaction is repeated for three times until the filtrate is neutral, then the filter cake is placed into a vacuum drying box for vacuum drying at 80 ℃ for 12h, the filter cake is taken out and ground after cooling, and the waste sponge-derived carbon-based solid acid loaded by sulfonic acid groups is obtained and recorded as 1SC650-3.
(2) Mixing CE-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave LG yield of 5.9% and LGO yield of 18.4%, as detailed in Table 1.
Example 3:
(1) The waste sponge is sent into a tube furnace, heated to 650 ℃ for carbonization for 3 hours at the heating rate of 10 ℃/min under inert atmosphere, and the reaction is naturally cooled after the reaction is finishedTaking out, grinding to 200 meshes, washing, filtering for three times, and vacuum drying the filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. Adding 1g of waste sponge derived porous carbon material into 5mL of dichloromethane, then adding 1g of chlorosulfonic acid (98%), turning over in a reaction kettle at 80 ℃ for reaction for 6h, washing with deionized water after the reaction is finished, filtering, repeating for three times until the filtrate is neutral, then placing the filter cake in a vacuum drying box, vacuum drying at 80 ℃ for 12h, cooling, taking out and grinding to obtain waste sponge derived carbon-based solid acid loaded by sulfonic acid groups, and recording as 1S Cl C650-3。
(2) Mixing CE-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave LG yield of 8.6% and LGO yield of 15.3%, as detailed in Table 1.
Example 4:
reference example 1 differs in that the biomass feedstock is tapioca.
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 650 ℃ under an inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is recorded as 1PC650-3.
(2) Mixing CA-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to the mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave an LG yield of 3.5% and an LGO yield of 24.5%, as detailed in Table 1.
Example 5:
reference example 1 was made with the difference that the biomass feedstock was bagasse.
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 650 ℃ under an inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is recorded as 1PC650-3.
(2) Mixing SU-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to the mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave an LG yield of 3.3% and an LGO yield of 23.9%, as detailed in Table 1.
Example 6:
reference example 1 was different in that the biomass feedstock was poplar dust.
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 650 ℃ under an inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is recorded as 1PC650-3.
(2) Mixing PO-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Heat of the bodyQualitative and quantitative analysis of the solution product by GC-MS gave LG yield of 3.7% and LGO yield of 21.2%, as detailed in Table 1.
Example 7:
(1) And (3) sending the waste sponge into a tubular furnace, carbonizing for 1 hour at the temperature rising rate of 10 ℃/min to 650 ℃ under inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water and 0.1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing and filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is marked as 0.1PC650-1.
(2) Mixing CE-50 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1: after 0.1 was uniformly mixed, the mixture was fed into a thermal cracker, and the temperature was raised to 350℃at a heating rate of 10℃per second and maintained for 10 seconds. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave LG yield of 1.8% and LGO yield of 0%, as detailed in Table 1.
Example 8:
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 450 ℃ under inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is marked as 1PC450-3.
(2) Mixing CE-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1: after 0.5 is evenly mixed, the mixture is sent into a thermal cracker, and the temperature is raised to 550 ℃ at a heating rate of 100 ℃/s and kept for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave an LG yield of 2.9% and an LGO yield of 13.2%, as detailed in Table 1.
Example 9:
(1) And (3) delivering the waste sponge into a tubular furnace, carbonizing for 3 hours at the temperature rising rate of 10 ℃/min to 750 ℃ under inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 1g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is recorded as 1PC750-3.
(2) Mixing CE-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:1 are evenly mixed and then are sent into a thermal cracker to 10 4 The temperature rise rate at C/s was raised to 750℃ and maintained for 20s. Qualitative and quantitative analysis of the pyrolysis product by GC-MS gave an LG yield of 3.0% and an LGO yield of 25.9%, as detailed in Table 1.
Example 10:
(1) And (3) sending the waste sponge into a tubular furnace, carbonizing for 6 hours at the temperature rising rate of 10 ℃/min to 850 ℃ under inert atmosphere, taking out and grinding to 200 meshes after the reaction is naturally cooled, washing and filtering for three times, and vacuum drying a filter cake at 80 ℃ for 12 hours to obtain the porous carbon material. To 1g of porous carbon material was added 10mL of deionized water with 2g of phosphoric acid (H 3 PO 4 85 wt.%) after 12h of ultrasonic dispersion, washing, filtering, repeating for three times, vacuum drying the filter cake at 80 ℃ for 12h, grinding, feeding the filter cake into a tube furnace, and activating at 500 ℃ for 2h under inert atmosphere to remove insufficiently combined phosphoric acid, thus obtaining waste sponge-derived carbon-based solid acid loaded by phosphate groups, which is marked as 2PC850-6.
(2) Mixing CE-200 particles with the carbon-based solid acid catalyst prepared in the step (1) according to a mass ratio of 1:2 are evenly mixed and then are sent into a thermal cracker, 10 4 The temperature rise rate at C/s was raised to 850℃ and maintained for 60s. Characterization of pyrolysis products by GC-MSThe LG yield was 0% and the LGO yield was 17.7% by quantitative analysis, as shown in Table 1
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 (8)
1. A method for converting waste sponge-derived carbon-based solid acid catalytic pyrolysis biomass into levoglucosan and levoglucosone, which is characterized by comprising the following steps:
(1) Washing, drying and crushing waste sponge from a scrapped car seat, feeding the waste sponge into a tube furnace, heating to 450-850 ℃ at a heating rate of 10 ℃/min under inert atmosphere, preserving heat for 1-6 hours, carbonizing the waste sponge, taking out and grinding the waste sponge after carbonizing, adding excessive deionized water, fully stirring and filtering the waste sponge, repeating the steps for three times, collecting a filter cake, drying the filter cake at 80 ℃ in vacuum for 12 hours, taking out the filter cake, and grinding the filter cake again to obtain the waste sponge-derived porous carbon material;
(2) And (3) loading the phosphate groups on the porous carbon material prepared in the step (1) by adopting an ultrasonic impregnation method, wherein the specific steps are as follows: adding the waste sponge-derived porous carbon material into deionized water, adding phosphoric acid, stirring and mixing, performing ultrasonic dispersion, washing with deionized water, filtering, repeating for three times, placing a filter cake in a vacuum drying oven, vacuum drying at 80 ℃ for 12 hours, cooling, taking out and grinding, then feeding the filter cake into a tubular furnace, and activating at 500 ℃ for 2 hours under an inert atmosphere to remove insufficiently-combined phosphoric acid, so as to obtain a waste sponge-derived carbon-based solid acid loaded by a phosphoric acid group;
or, loading the porous carbon material prepared in the step (1) with sulfonic acid groups by adopting a hydrothermal impregnation method, wherein the specific steps are as follows: adding a waste sponge derived porous carbon material into dichloromethane, then adding sulfuric acid or chlorosulfonic acid, turning over in a reaction kettle at 50-100 ℃ for reaction for 6 hours, washing with deionized water and filtering after the reaction is finished, repeating for three times until the filtrate is neutral, then placing a filter cake in a vacuum drying box, vacuum drying at 80 ℃ for 12 hours, cooling, taking out and grinding to obtain a sulfonic acid group-loaded waste sponge derived carbon-based solid acid;
(3) Mixing the acid-loaded waste sponge-derived carbon-based solid acid prepared in the step (2) serving as a catalyst with a biomass raw material, and then placing the mixture into a fine quartz tube for catalytic pyrolysis reaction, wherein the mass ratio of the biomass raw material to the waste sponge-derived carbon-based solid acid catalyst is 1:0.1 to 2, the temperature rising rate is 10 to 10 4 The pyrolysis temperature is 350-850 ℃ and the pyrolysis heat preservation time is 10-60 s.
2. The method according to claim 1, wherein the mass ratio of phosphoric acid or sulfuric acid or chlorosulfonic acid to the waste sponge-derived porous carbon material is 0.1 to 2.
3. The method of claim 1, wherein the biomass raw material in the step (3) is one of cellulose with 50-200 meshes, tapioca, bagasse and poplar powder.
4. The method according to claim 1, wherein the porous carbon material prepared in step (1) is loaded with sulfonic acid groups by a hydrothermal impregnation method at a temperature of 75 to 85 ℃.
5. The method of claim 4, wherein the temperature is 80 ℃.
6. The method according to claim 1, wherein the carbonization temperature in step (1) is 550 to 650 ℃.
7. The process of claim 1, wherein the pyrolysis temperature in step (3) is 550 to 800 ℃.
8. The process of claim 1, wherein the pyrolysis temperature of step (3) is 750 ℃.
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