CN116371428B - Solid acid catalyst for depolymerizing waste plastics and preparation method thereof - Google Patents
Solid acid catalyst for depolymerizing waste plastics and preparation method thereof Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004033 plastic Substances 0.000 title abstract description 34
- 229920003023 plastic Polymers 0.000 title abstract description 34
- 239000002699 waste material Substances 0.000 title abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 149
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000013543 active substance Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000004523 catalytic cracking Methods 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 31
- 238000000967 suction filtration Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003763 carbonization Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- 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
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of solid acid catalysts, in particular to a solid acid catalyst for depolymerizing waste plastics and a preparation method thereof, which adopts the following scheme that the solid acid catalyst is prepared by carrying a catalytic active component by using activated carbon subjected to surface modification to obtain a precursor and calcining the precursor, wherein the surface modification step of the activated carbon comprises the following steps: and (3) soaking the activated carbon in an alkaline solution, filtering to obtain alkali modified activated carbon, and loading nano silicon dioxide on the alkali modified activated carbon to obtain the surface modified activated carbon. The efficiency of catalytic cracking of waste plastics by using the surface-modified active carbon-supported catalytic active substance (SO 4 2‑/ZrO2) is higher than that of pure SO 4 2‑/ZrO2 solid acid, and the surface-modified active carbon has a large specific surface area, SO that the reaction contact area of the catalytic active component is greatly increased, the reaction point is increased, the release of H + in water is accelerated, the active component is facilitated to attack the chain segment of the high-molecular polymer, and the cracking of the high-molecular polymer is promoted.
Description
Technical Field
The invention relates to the field of solid acid catalysts, in particular to a solid acid catalyst for depolymerizing waste plastics and a preparation method thereof.
Background
The plastic product consumption is large in China, the apparent consumption of plastic per year is over hundred million tons in China according to statistics of China's renewable materials society, the yield of waste plastic is over 7000 ten thousand tons, 32% of the waste plastic is buried, 31% of the waste plastic is burned, 37% of the waste plastic is abandoned, and the recycling rate is very low, so that the ecological environment is polluted and destroyed, and a large amount of resource waste is caused. In this context, recycling of waste plastics is proposed in all countries of the world, in which depolymerization of waste plastics into monomers by chemical methods is critical, with regard to the yield and quality of recycled plastics.
For environmental protection, the depolymerization of waste plastics such as polyester, nylon and the like by using solid acid is already a worldwide accepted recovery method with the most industrialization prospect. However, the yield of the target product of the depolymerization of the waste plastic catalyzed by the solid acid is low at present mainly because the specific surface area of the adopted solid acid such as 12-phosphotungstic acid, SO 4 2-/ZrO2 and the like is small, the specific surface area is only 20-150m 2/g, the reaction contact is insufficient, the release of H+ by hydrolysis is less, the active components are difficult to attack the high polymer dissolved in water, the unreacted high polymer in the product is more, and the final regenerated product has low yield and poor quality.
Therefore, the invention provides a solid acid catalyst for depolymerizing waste plastics and a preparation method thereof.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a solid acid catalyst for depolymerizing waste plastics and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The first aspect of the invention provides a preparation method of a solid acid catalyst for depolymerizing waste plastics, which comprises the steps of carrying a catalytic active component by using activated carbon subjected to surface modification to obtain a precursor, and calcining the precursor to obtain the solid acid catalyst.
Further, the surface modification step of the activated carbon comprises: and (3) soaking the activated carbon in an alkaline solution, filtering to obtain alkali modified activated carbon, and loading nano silicon dioxide on the alkali modified activated carbon to obtain the surface modified activated carbon.
Further, the alkaline solution comprises 0.5-2mol/L NaOH solution and 0.4-1.5mol/L KOH solution, and the soaking time comprises 1-3h.
Further, the preparation step of the precursor comprises the following steps: and (3) placing the surface modified activated carbon in ZrOCl 2.8H2O solution for soaking for 2-3 hours, filtering, placing filter residues in an acid solution for soaking for 20-40 minutes, and filtering to obtain a precursor.
Further, the calcination temperature of the precursor is 600-800 ℃ and the calcination time is 1-2 hours.
Further, the acidic solution comprises a sulfuric acid solution or a phosphoric acid solution with a solubility of 5-20%, and the preparation steps of the surface-modified activated carbon comprise: immersing the alkali modified activated carbon in water, adding nano silicon dioxide, stirring at 600-900rpm for 0.8-1.5h, filtering, and taking filter residues to obtain the surface modified activated carbon.
Further, the activated carbon is oxidized activated carbon, and the preparation steps of the oxidized activated carbon include: calcining the resin particles to obtain carbonized particles, activating the carbonized particles by a steam activation method to obtain activated carbon, and immersing the activated carbon in a hydrogen peroxide solution to obtain oxidized activated carbon.
Further, the resin particles comprise phenolic resin particles, the phenolic resin particles are calcined at 500-700 ℃ for 1-2 hours to obtain carbonized particles, the activation time of the carbonized particles is 20-40min, the activation temperature is 800-1000 ℃ to obtain activated carbon, and the activated carbon is immersed in 5-15% hydrogen peroxide solution for 1-1.5 hours.
Further, each material comprises the following components in parts by weight: 30-40 parts of oxidized active carbon, 8-15 parts of nano silicon dioxide and 5-12 parts of ZrOCl 2·8H2 O.
The second aspect of the invention provides a solid acid catalyst for depolymerizing waste plastics, which is prepared by the method.
The invention has the beneficial effects that:
1. The efficiency of catalytically cracking waste plastics by using the surface-modified active carbon-supported catalytic active substances (SO 4 2-/ZrO2) is higher than that of pure SO 4 2-/ZrO2 solid acid, because the surface-modified active carbon has a large specific surface area, the reaction contact area of the catalytic active components is greatly increased, the reaction sites are increased, the release of H + in water is accelerated, the active components are also favorable for attacking chain segments of the high-molecular polymer, and the cracking of the high-molecular polymer is promoted;
2. The alkaline solution is used for etching the surface of the active carbon, so that the pore diameter of pores on the surface of the active carbon and the surface area of the pores are increased, the active carbon is enabled to load more active components, and the reaction contact area of the catalytic active components is greatly increased;
3. the nano silicon dioxide is loaded on the pore surfaces of the active carbon, so that on one hand, the heat resistance of the active carbon and the catalytic active substances during high-temperature calcination is improved, the performance of the active carbon and the catalytic active substances during high-temperature calcination is reduced, on the other hand, the nano silicon dioxide provides a loading surface, and a part of the catalytic active substances is loaded on the surface of the silicon dioxide, so that the active carbon loads more active components, and the reaction contact area of the catalytic active components is greatly increased.
Drawings
FIG. 1 is a schematic diagram of the mechanism of the active carbon-supported catalytic active material of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
In the following examples, the particle size of the nano-silica is 10-20nm, the alkaline solution is 0.5-2mol/L sodium hydroxide solution, the raw material of the oxidized active carbon is phenolic resin particles, the suction filtration adopts a nano-grade filter membrane of 50nm, and the acidic solution is sulfuric acid solution.
Example 1
(1) Placing 200g of phenolic resin particles into a tubular resistance furnace for calcination until carbonization, wherein the temperature is 500 ℃, and the calcination time is 1h to obtain carbonized particles;
(2) The carbonized particles are put into a carbonization furnace and activated for 1.5 hours under the water vapor at 800 ℃ to obtain activated carbon;
(3) Immersing activated carbon in a hydrogen peroxide solution with the concentration of 5%, and treating for 1 hour to obtain oxidized activated carbon;
(4) Weighing 30g of oxidized active carbon, soaking in 90mL of 0.5mol/L sodium hydroxide solution for 1h, carrying out suction filtration, and washing the filter residue product of the suction filtration with deionized water for 3 times to obtain alkali modified active carbon;
(5) Placing alkali modified activated carbon into a beaker containing 200mL of water, adding 8g of nano silicon dioxide, stirring for 0.8h by using a magnetic stirrer at 600, carrying out suction filtration, taking filter residues, and drying in a 60 ℃ oven for 0.8h to obtain activated carbon (surface modified activated carbon) loaded with the silicon dioxide;
(6) Weighing 5g of ZrOCl 2·8H2 O, adding deionized water to dilute the ZrOCl 2·8H2 O into 60mL of ZrOCl 2·8H2 O solution, placing the surface modified activated carbon into ZrOCl 2.8H2O solution, soaking the activated carbon for 2 hours, and filtering to obtain filter residues;
(7) And (3) placing filter residues in 50mL of 5% sulfuric acid solution, soaking for 20min, filtering, taking a filter residue product, taking out the product, placing the product into a muffle furnace, and calcining at a high temperature of 600 ℃ for 1 hour to obtain the solid acid catalyst.
Example 2
(1) Placing 200g of phenolic resin particles into a tubular resistance furnace for calcination until carbonization, wherein the temperature is 600 ℃, and the calcination time is 1.5h to obtain carbonized particles;
(2) The carbonized particles are put into a carbonization furnace and activated for 1.8 hours under the water vapor of 900 ℃ to obtain activated carbon;
(3) Immersing activated carbon in a hydrogen peroxide solution with the solution concentration of 10%, and treating for 1.2 hours to obtain oxidized activated carbon;
(4) Weighing 35g of oxidized active carbon, soaking in 95mL of 1mol/L sodium hydroxide solution for 2 hours, carrying out suction filtration, and washing the filter residue product of the suction filtration with deionized water for 3 times to obtain alkali modified active carbon;
(5) Placing alkali modified activated carbon into a beaker containing 200mL of water, adding 12g of nano silicon dioxide, stirring for 1h at 800rpm by using a magnetic stirrer, carrying out suction filtration, taking filter residues, and drying in a 70 ℃ oven for 1h to obtain activated carbon (surface modified activated carbon) loaded with the silicon dioxide;
(6) 8g of ZrOCl 2·8H2 O was weighed, deionized water was added to dilute into 70mL of ZrOCl 2·8H2 O solution, and the surface-modified activated carbon was placed in Soaking in the solution for 2.5h, filtering, and collecting residue;
(7) And (3) placing filter residues in 50mL of 15% sulfuric acid solution, soaking for 30min, filtering, taking a filter residue product, taking out the product, placing the product into a muffle furnace, and calcining at a high temperature of 700 ℃ for 1.5h to obtain the solid acid catalyst.
Example 3
(1) Placing 200g of phenolic resin particles into a tubular resistance furnace for calcination until carbonization, wherein the temperature is 700 ℃, and the calcination time is 2 hours to obtain carbonized particles;
(2) The carbonized particles are put into a carbonization furnace and activated for 2 hours under the water vapor at 1000 ℃ to obtain activated carbon;
(3) Immersing activated carbon in a hydrogen peroxide solution with the solution concentration of 15%, and treating for 1.5 hours to obtain oxidized activated carbon;
(4) Weighing 40g of oxidized active carbon, soaking in 100mL of 2mol/L sodium hydroxide solution for 3 hours, carrying out suction filtration, and washing a filter residue product of the suction filtration with deionized water for 3 times to obtain alkali modified active carbon;
(5) Placing alkali modified activated carbon into a beaker containing 200mL of water, adding 15g of nano silicon dioxide, stirring for 1.5h at 900rpm by using a magnetic stirrer, carrying out suction filtration, taking filter residues, and drying in an oven at 80 ℃ for 1.5h to obtain activated carbon (surface modified activated carbon) loaded with the silicon dioxide;
(6) 12g of ZrOCl 2·8H2 O was weighed, deionized water was added to dilute into 90mL of ZrOCl 2·8H2 O solution, and the surface-modified activated carbon was placed in Soaking in the solution for 3 hours, filtering, and taking filter residues;
(7) And (3) placing filter residues in 50mL of 20% sulfuric acid solution, soaking for 40min, filtering, taking a filter residue product, taking out the product, placing the product into a muffle furnace, and calcining at a high temperature of 800 ℃ for 2 hours to obtain the solid acid catalyst.
Comparative example 1 (comparative example 3 without silica added)
(1) Placing 200g of phenolic resin particles into a tubular resistance furnace for calcination until carbonization, wherein the temperature is 700 ℃, and the calcination time is 2 hours to obtain carbonized particles;
(2) The carbonized particles are put into a carbonization furnace and activated for 2 hours under the water vapor at 1000 ℃ to obtain activated carbon;
(3) Immersing activated carbon in a hydrogen peroxide solution with the solution concentration of 15%, and treating for 1.5 hours to obtain oxidized activated carbon;
(4) Weighing 40g of oxidized active carbon, soaking in 100mL of 2mol/L sodium hydroxide solution for 3 hours, carrying out suction filtration, and washing a filter residue product of the suction filtration with deionized water for 3 times to obtain alkali modified active carbon;
(5) 12g of ZrOCl 2·8H2 O was weighed, deionized water was added to dilute into 90mL of ZrOCl 2·8H2 O solution, and the alkali modified activated carbon was placed in Soaking in the solution for 3 hours, filtering, and taking filter residues;
(6) And (3) placing filter residues in 50mL of 20% sulfuric acid solution, soaking for 40min, filtering, taking a filter residue product, taking out the product, placing the product into a muffle furnace, and calcining at a high temperature of 800 ℃ for 2 hours to obtain the solid acid catalyst.
Comparative example 2 (compared to example 3, no surface modification of activated carbon was performed)
(1) Placing 200g of phenolic resin particles into a tubular resistance furnace for calcination until carbonization, wherein the temperature is 700 ℃, and the calcination time is 2 hours to obtain carbonized particles;
(2) The carbonized particles are put into a carbonization furnace and activated for 2 hours under the water vapor at 1000 ℃ to obtain activated carbon;
(3) Immersing activated carbon in a hydrogen peroxide solution with the solution concentration of 15%, and treating for 1.5 hours to obtain oxidized activated carbon;
(4) Weighing 12g of ZrOCl 2·8H2 O, adding deionized water to dilute into 90mL of ZrOCl 2·8H2 O solution, placing oxidized active carbon into the ZrOCl 2·8H2 O solution, soaking for 3 hours, filtering, and taking filter residues;
(5) And (3) placing filter residues in 50mL of 20% sulfuric acid solution, soaking for 40min, filtering, taking a filter residue product, taking out the product, placing the product into a muffle furnace, and calcining at a high temperature of 800 ℃ for 2 hours to obtain the solid acid catalyst.
Experimental example
The solid acid catalysts prepared in examples 1-3 and comparative examples 1-2 were ground to a sieve of 800 mesh to obtain powdery solid acid catalysts, and waste plastic (nylon) catalytic cracking experiments were carried out in a batch reactor by taking 1g of the powdery solid acid catalysts in examples 1-3 and comparative examples 1-2 and 1g of SO 4 2-/ZrO2 solid acid, respectively, according to the following experimental methods.
10G of nylon waste plastic chips were charged into a 250ml reactor, and 1g of a powdery solid acid catalyst was added. The reactor is closed, the reaction temperature is increased to 300 ℃, and the stirring function is started when the plastic starts to melt, so as to perform the catalytic cracking reaction of the plastic. The produced low boiling point organic product is discharged from the outlet of the reactor, liquid products are collected by cold trap condensation, gaseous products below C5 are collected by adopting a gas collecting bottle, and the reaction time is based on the condition that the liquid products cannot be collected. The respective yields were calculated from the resulting liquid oil, solid content and gaseous product weight, and qualitative and quantitative analysis of the product components were performed on a QP-2010 GC-MS chromatograph-mass spectrometer. The results are shown in Table 1:
TABLE 1 catalytic cracking solids content and product content of plastics
From the data in the above tables, it can be concluded that examples 1-3, in which the liquid oil content of the cracking product is gradually increased, the residual amount of plastic solids is gradually decreased, and the gaseous product is substantially stable: with the change of reaction conditions and the increase of the consumption of reactants, the catalytic performance of the prepared powdery solid acid catalyst is gradually improved;
Comparing the data of example 3 with the data of SO 4 2-/ZrO2 solid acid, the solid content of the plastic obtained by catalytic cracking of the powdery solid acid catalyst of example 3 is 29%, the solid content of the plastic obtained by catalytic cracking of the solid acid of SO 4 2-/ZrO2 is 39%, and the content of the catalytically active component ZrO 2 in the powdery solid acid catalyst of example 3 is smaller than the content of ZrO 2 in the solid acid of SO 4 2-/ZrO2, SO that the catalytic efficiency of catalytic cracking of waste plastics by using the surface-modified active carbon-supported catalytically active substance (SO 4 2-/ZrO2) is higher than that of the pure SO 4 2-/ZrO2 solid acid, because the surface-modified active carbon has a large specific surface area, the reaction contact area of the catalytically active component is greatly increased, the reaction sites are increased, the release of H + in water is accelerated, the active component is also favorable for attacking the chain segments of the high-molecular polymer, and the cracking of the high-molecular polymer is promoted;
comparing the data of comparative example 1 and comparative example 2, the residual content of the solid of the plastic catalytically cracked by the powdery solid acid catalyst of comparative example 1 is 45%, and the residual content of the solid of the plastic catalytically cracked by the solid acid of comparative example 2 is 53%, it can be seen that the catalytic efficiency of the catalytic active substance supported by the activated carbon modified by the alkali is higher than that of the catalytic active substance supported by the unmodified activated carbon, because the surface of the activated carbon is etched by the alkaline solution, the pore diameter of the pores and the surface area of the pores on the surface of the activated carbon are increased, so that the activated carbon supports more active components, and the reaction contact area of the catalytic active components is greatly increased;
Comparing the data of example 3 with the data of comparative example 1, the solid content of the plastic catalytically cracked by the powdery solid acid catalyst of example 3 is 29%, and the solid content of the plastic catalytically cracked by the solid acid of comparative example 1 is 45%, it can be seen that the addition of nano silica improves the catalytic efficiency of the catalyst because the nano silica is supported on the pore surfaces of the activated carbon, on the one hand, improves the heat resistance of the activated carbon and the catalytic active substance during high-temperature calcination, reduces the reduced performance of the activated carbon and the catalytic active substance during high-temperature calcination, and on the other hand, the nano silica provides a supporting surface, and a part of the catalytic active substance is supported on the surface of the silica, so that the activated carbon supports more active component, and the reaction contact area of the catalytic active component is greatly increased.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. A preparation method of a solid acid catalyst is characterized in that: the method comprises the steps of loading a catalytic active component by using surface-modified active carbon to obtain a precursor, and calcining the precursor to obtain a solid acid catalyst; the surface modification step of the activated carbon comprises the following steps: soaking and filtering the activated carbon in alkaline solution to obtain alkali modified activated carbon, immersing the alkali modified activated carbon in water, adding nano silicon dioxide, stirring at 600-900rpm for 0.8-1.5h, filtering, and taking filter residues to obtain surface modified activated carbon; the active carbon is oxidized active carbon, and the preparation steps of the oxidized active carbon comprise: calcining the resin particles to obtain carbonized particles, activating the carbonized particles by a steam activation method to obtain activated carbon, and immersing the activated carbon in a hydrogen peroxide solution to obtain oxidized activated carbon; the alkaline solution comprises 0.5-2mol/L NaOH solution and 0.4-1.5mol/L KOH solution, and the soaking time comprises 1-3 hours; the preparation steps of the precursor comprise: soaking surface modified activated carbon in ZrOCl 2·8H2 O solution for 2-3h, filtering, soaking the filter residue in acidic solution for 20-40min, and filtering to obtain precursor; the acid solution comprises sulfuric acid solution or phosphoric acid solution with the concentration of 5-20%; the calcination temperature of the precursor is 600-800 ℃ and the calcination time is 1-2 hours.
2. The method for preparing a solid acid catalyst according to claim 1, wherein the resin particles comprise phenolic resin particles, the phenolic resin particles are calcined at 500-700 ℃ for 1-2 hours to obtain carbonized particles, the activation time of the carbonized particles is 20-40min, the activation temperature is 800-1000 ℃ to obtain activated carbon, and the activated carbon is immersed in a 5-15% hydrogen peroxide solution for 1-1.5 hours.
3. The method for preparing a solid acid catalyst according to claim 2, wherein the solid acid catalyst comprises the following substances in parts by weight: 30-40 parts of oxidized active carbon, 8-15 parts of nano silicon dioxide and 5-12 parts of ZrOCl 2·8H2 O.
4. A solid acid catalyst prepared by the method for preparing a solid acid catalyst according to any one of claims 1 to 3.
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