Method for preparing high-quality gas-liquid product by catalytically pyrolyzing aquatic plant garbage through Al2O3-based platinum leaching waste residues

Abstract

The invention discloses a method for preparing a high-quality gas-liquid product by catalytically pyrolyzing aquatic plant garbage through Al2O3-based platinum leaching waste residues, and relates to the field of efficient utilization of biomass energy. Comprising the following steps: respectively drying, crushing and sieving the aquatic plant garbage and the platinum leaching waste residues to obtain aquatic plant garbage powder and waste residue powder, and uniformly mixing the aquatic plant garbage powder and the waste residue powder; and carrying out rapid pyrolysis on the pyrolysis raw material obtained by pressing the mixed powder in an inert atmosphere to obtain high-selectivity furfural bio-oil and synthesis gas. According to the method, high-quality bio-oil and synthesis gas are used as target products, aquatic plant garbage biomass is used as a raw material, Al2O3-based platinum catalyst leaching residues are used as a catalyst, catalytic active sites of platinum metal and Al2O3 acidic sites in the waste platinum leaching residues are efficiently utilized, and the catalytic activity of the waste platinum leaching residues is improved. And the aquatic plant garbage is catalytically and rapidly pyrolyzed to obtain a liquid-phase product rich in furfural and synthesis gas rich in combustible gas, so that the selectivity of the furfural and the combustible gas is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of efficient utilization of biomass energy, and in particular to a method for preparing high-quality bio-oil and synthesis gas by catalytic pyrolysis of aquatic plant waste by using Al2O3-based platinum leaching waste residue. Background Art

[0002] Through advanced biological, chemical or thermochemical conversion technologies, biomass can be efficiently converted into biofuels, platform chemicals and high-performance bio-based materials to meet the growing demand for energy and material substitution. Among them, furfural is considered to be one of the most important platform chemicals. It is the only biomass-derived organic compound that can replace crude oil organic compounds used in industry. However, the current selectivity of furfural produced by hydrolyzing corn cobs can reach up to 75.27%. Synthesis gas is an important derivative product of the biomass thermal conversion process. Since biomass mainly exists in the form of C elements, the gas after pyrolysis is usually mainly CO2, which will result in lower quality of synthesis gas, and CO2 is one of the culprits of the greenhouse effect.

[0003] Aquatic plant waste is a kind of biomass, usually including aquatic plant residues, algae, invasive plants, etc. As aquatic plant waste, aquatic plant residues will aggravate the eutrophication of water bodies and accelerate the swamping of lakes. Most algae or invasive plants can proliferate and expand rapidly (100 to 120 tons per hectare of water per year) and have strong environmental adaptability, causing great damage to the environment and ecological balance. However, the current treatment methods are limited, and most of them can only be landfilled or incinerated, and both methods may cause secondary pollution to the environment. In addition, the extremely fast reproduction speed of aquatic plant waste is also widely used as a raw material for rapid pyrolysis.

[0004] In the oil refining process, fluid catalytic cracking will produce a large amount of waste catalytic cracking slag, which contains metals such as Pt and Pd and has a very high potential for reuse. In the face of this part of precious resources, the current main recovery methods are physical separation, chemical regeneration and acid treatment, aiming to efficiently extract this part of precious metals. The platinum leaching waste slag after the precious metals are extracted by acid treatment technology still contains a small amount of precious metals, but is usually landfilled or made into bricks. This treatment method is a waste of precious metals with catalytic potential in the platinum leaching waste slag. Therefore, the reuse of Al2O3-based platinum catalyst leaching waste slag can not only improve the secondary utilization rate of waste resources, but also further prepare high value-added products. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing high-quality bio-oil and synthesis gas by catalytic pyrolysis of aquatic plant waste biomass by Al2O3-based platinum leaching waste residue, using aquatic plant waste biomass as raw material and Al2O3-based platinum catalyst leaching waste residue as catalyst, efficiently utilizing the Pt metal active catalytic sites and Al2O3 acid sites in the waste platinum leaching residue, catalytically and rapidly pyrolyzing the aquatic plant waste biomass to obtain a liquid phase product with high furfural selectivity and high-quality combustible gas.

[0006] To achieve the above object, the present invention provides a method for preparing furfural by catalytic pyrolysis of aquatic plant waste by Al2O3-based platinum leaching waste residue, comprising the following steps:

[0007] (1) drying, crushing and sieving the aquatic plant garbage and Al2O3-based platinum leaching waste residue respectively to obtain aquatic plant garbage biomass powder and Al2O3-based platinum leaching waste residue powder for standby use;

[0008] (2) mixing the aquatic plant waste biomass powder and the Al2O3-based platinum leaching waste residue powder uniformly to obtain a mixed powder;

[0009] (3) pressing the mixed powder to obtain a pressed raw material;

[0010] (4) Under an inert atmosphere, the pressed raw material is rapidly pyrolyzed, and after the pyrolysis is completed, non-condensable components, condensable components and biochar are obtained;

[0011] (5) After condensing the condensable components, a bio-oil with high selectivity for furfural is obtained, and the non-condensable components are combustible synthesis gas.

[0012] Specifically, the Al2O3-based platinum leaching waste residue produced in the process of extracting precious metals with platinum catalyst acid leaching is used as a catalyst for the pyrolysis process of aquatic plant waste biomass. After the catalytic pyrolysis is completed, the proportion of liquid products can reach up to 71%. After GC-MS analysis, the furfural selectivity in the liquid products is as high as 97%; the gas products are analyzed by GC, and the combustible gas content is as high as 88%. The liquid products are condensed with ice-water mixtures to obtain pyrolysis oil with high furfural selectivity by collecting the volatiles.

[0013] Specifically, aquatic plant waste produces solid, liquid and gas three-phase products under high temperature catalytic pyrolysis, the gas phase is a non-condensable component, the liquid phase is a condensable component, and the solid phase is carbon; the condensable component is condensed by using an ice-water mixture to collect bio-oil with high furfural selectivity. The present invention utilizes the Pt metal active sites with catalytic effects and the Al2O3 acid sites in the waste residue to catalyze the pyrolysis of aquatic plant waste biomass, and obtains a liquid phase product with up to 97% furfural selectivity and a combustible gas content of 95%, and realizes the coordinated utilization of waste.

[0014] During pyrolysis, the hot pressed raw materials are placed in a quartz tube, and quartz wool is placed in the quartz tube to ensure that the raw materials are located in the constant temperature range (400-800°C) of the vertical tube furnace, and an inert atmosphere is introduced. The temperature of the vertical tube furnace is set, and when the required temperature is reached, the quartz tube is placed in the tube furnace to start collecting the three-phase products produced.

[0015] Preferably, the aquatic plant garbage in step (1) is one or more of water hyacinth, lotus shell, lotus leaf or aquatic plant residues.

[0016] Preferably, the drying temperature in step (1) is 60-115° C., and the drying time is 12-24 h; and the sieving is through a 50-200 mesh sieve.

[0017] Preferably, in step (2), the mass ratio of the aquatic plant waste biomass powder to the Al2O3-based platinum leaching waste residue powder is 1:0.5-5.

[0018] Preferably, the pressing intensity during hot pressing in step (3) is 7 MPa and the pressing time is 1 min.

[0019] Preferably, the diameter of the pressed raw material in step (3) is 8 to 12 mm.

[0020] Preferably, the pyrolysis temperature in step (4) is 400-800° C., and the pyrolysis time is 5-30 min.

[0021] Preferably, the inert atmosphere in step (4) is nitrogen or argon, with a flow rate of 50 to 200 mL / min.

[0022] The beneficial effects of the present invention are:

[0023] (1) The present invention provides a new way to recycle two types of waste, namely, aquatic plant waste and Al2O3-based platinum leaching waste residue. Aquatic plant waste biomass is used as raw material, and waste residue generated in the process of platinum catalyst acid leaching to extract precious metals is used as a catalyst to prepare furfural. At the same time, the gas phase (combustible gas) and solid phase (biochar) obtained by pyrolysis can be used as a reducing agent for extracting precious metals from platinum catalyst acid leaching residue, which greatly reduces costs and improves economic benefits.

[0024] (2) The present invention adopts a catalytic rapid pyrolysis method, optimizes relevant reaction parameters, and utilizes the catalytic factors in the Al2O3-based waste platinum leaching residue. Compared with the 70% selectivity of the traditional method of preparing furfural by hydrolysis and acid catalysis, the selectivity of furfural is increased to 97% and the combustible gas content is increased to 95% through catalytic rapid pyrolysis.

[0025] (3) The invention adds Al2O3-based waste platinum leaching residue as a catalyst, and the proportion of liquid products increases from 43% to 71%, which significantly increases the proportion of liquid products.

[0026] (4) The furfural obtained by the present invention is one of the most important platform chemicals, with a furfural selectivity of up to 97%, and can be widely used as an intermediate for synthesizing chemicals, synthetic resins, dyes, medicines, pesticides, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a process flow chart of the present invention.

[0028] Figure 2 This is a BET adsorption-desorption curve diagram of platinum leaching waste residue of the present invention;

[0029] Figure 3 It is a point-line diagram of pyridine-infrared adsorption of platinum leaching waste residue of the present invention;

[0030] Figure 4 It is a dot-line diagram of liquid products with different waste residue ratios obtained in Examples 6, 7, 8, 9, 10 and 11 of the present invention;

[0031] Figure 5 is a dotted line graph of GC-MS furfural selectivity at different waste residue ratios obtained in Examples 6, 7, 8, 9, 10, and 11 of the present invention;

[0032] Figure 6 It is a dot-line graph of GC combustible gas yields at different waste residue ratios obtained in Examples 6, 7, 8, 9, 10 and 11 of the present invention. DETAILED DESCRIPTION

[0033] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limitations of the present invention. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0034] The platinum leaching waste residue used in the following examples is: During the petroleum refining process, fluid catalytic cracking will produce a large amount of waste catalytic cracking slag, which usually contains precious metals such as Pd and Pt. The platinum leaching waste residue remaining after the waste catalytic cracking slag is treated with acid leaching with hydrochloric acid, sodium chlorate, etc. to extract precious metals from the slag is used as the raw material.

[0035] The BET adsorption-desorption curve of platinum leaching waste residue is as follows: Figure 2 As shown by Figure 2 It can be seen that the pore size of the waste residue has undergone single-layer-multilayer adsorption and capillary condensation phenomena, and has a hysteresis loop, which belongs to a mesoporous structure.

[0036] The obtained Pt leaching waste residue pyridine-infrared adsorption point line diagram is as follows Figure 3 As shown by Figure 3 It can be seen that at 1450cm -1 There is a very high peak at 1550cm, indicating that the waste residue contains a lot of L acid sites, and a small amount of B acid at the corresponding 1550cm -1 Place.

[0037] The above characteristics indicate that platinum leaching waste residue can be used as a catalyst.

[0038] Example 1

[0039] like Figure 1 As shown, the method for preparing furfural with high selectivity by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0040] (1) Dry the aquatic plant waste - water hyacinth in a drying oven at 105°C for 12 hours, grind it through a grinder and pass it through a 100-mesh sieve for later use.

[0041] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1), put it into an 11 mm grinding tool, and use a hot press to press the raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0042] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0043] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0044] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 43%. After GC-MS analysis, there was no furfural product peak in the liquid products. After GC analysis, the proportion of combustible gases in the gas products was only 10%, including CO and CH4.

[0045] It can be seen that if the platinum catalyst acid leaching waste residue is not used as a catalyst, furfural product cannot be prepared.

[0046] Example 2

[0047] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0048] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0049] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool and use a press to obtain the pressed raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0050] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0051] (4) The temperature of the tubular furnace is set to 400°C. After the temperature reaches 400°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0052] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 47%, and the peak area of ​​furfural in the liquid products could reach 51% after GC-MS analysis. After GC analysis, the combustible gas in the gas products accounted for 70%, including CO, CH4, C2H4, and H2.

[0053] Example 3

[0054] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0055] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0056] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 12.5 g of waste platinum leaching residue, put them into an 11 mm grinding tool, and use a hot press to press the raw materials. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0057] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0058] (4) The temperature of the tubular furnace is set to 600°C. After the temperature reaches 600°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0059] After the catalytic pyrolysis experiment in the above process, the yield of liquid products is 65%. According to GC-MS analysis, the furfural peak area in the liquid products can reach 84%. According to GC analysis, the combustible gas in the gas products accounts for 75%, including CO, CH4, H2, and C2H4.

[0060] Example 4

[0061] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0062] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0063] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue, put them into an 11 mm grinding tool, and press the raw materials using a hot press, with a pressing strength of 7 MPa and a pressing time of 1 min.

[0064] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0065] (4) The temperature of the tubular furnace is set to 700°C. After the temperature reaches 700°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0066] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 61%. According to GC-MS analysis, the furfural peak area in the liquid products can reach 81%. According to GC analysis, the combustible gas in the gas products accounted for 77%, including CO, H2, CH4, and C2H4.

[0067] Example 5

[0068] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0069] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0070] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue, put them into an 11 mm grinding tool, and press the raw materials using a hot press, with a pressing strength of 7 MPa and a pressing time of 1 min.

[0071] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0072] (4) The temperature of the tubular furnace is set to 800°C. After the temperature reaches 800°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0073] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 56%. According to GC-MS analysis, the furfural peak area in the liquid products can reach 77%. According to GC analysis, the combustible gas in the gas products accounted for 82%, including CO, H2, CH4, and C2H4.

[0074] Example 6

[0075] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0076] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0077] (2) Take 5 g of the aquatic plant waste biomass raw material obtained in step (1) and 5 g of Al2O3-based waste platinum leaching residue. Mix them evenly and put them into an 11 mm grinding tool. Use a hot press to press the raw materials. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0078] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0079] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0080] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 54%. After GC-MS analysis, the furfural peak area in the liquid products can reach 57%. After GC analysis of the gas products, the proportion of combustible gases reached 80%, including CO, H2, CH4, and C2H4.

[0081] Example 7

[0082] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0083] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0084] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 10 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool, and use a hot press to press the raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0085] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0086] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0087] After the catalytic pyrolysis experiment in the above process, the yield of liquid products is 65%. According to GC-MS analysis, the furfural peak area in the liquid products can reach 87%. According to GC analysis, the proportion of combustible gases in the gas products can reach 84%, including CO, H2, CH4, and C2H4.

[0088] Example 8

[0089] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0090] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0091] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool and press the raw material by hot pressing. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0092] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0093] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0094] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 69%. After GC-MS analysis, the selectivity of furfural in the liquid products could reach 96%. After GC analysis of the gas products, the proportion of combustible gases could reach 88%, including CO, H2, C2H4, and CH4.

[0095] Example 9

[0096] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0097] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0098] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 15 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool, and use a hot press to press the raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0099] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0100] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0101] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 71%. After GC-MS analysis, the furfural peak area in the liquid products can reach 97%. After GC analysis of the gas products, the proportion of combustible gases can reach 87%, including CO, H2, C2H4, and CH4.

[0102] Example 10

[0103] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0104] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0105] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 20 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool, and use a hot press to press the raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0106] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0107] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0108] After the catalytic pyrolysis experiment in the above process, the yield of liquid products is 68%. According to GC-MS analysis, the furfural peak area in the liquid products can reach 95%. According to GC analysis of the gas products, the proportion of combustible gases can reach 85%, including CO, H2, C2H4, and CH4.

[0109] Embodiment 11

[0110] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0111] (1) Dry the aquatic plant waste (water hyacinth) and Al2O3-based waste platinum leaching residue in a drying oven at 105°C for 12 hours, grind it through a 100-mesh sieve with a grinder and set it aside.

[0112] (2) Take 5 g of the water hyacinth biomass raw material obtained in step (1) and 25 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 11 mm grinding tool, and use a hot press to press the raw material. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0113] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 100 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0114] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 15 minutes, the solid products are collected.

[0115] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 66%. After GC-MS analysis, the furfural peak area in the liquid products can reach 94%. After GC analysis of the gas products, the proportion of combustible gases can reach 83%, including CO, H2, CH4, C2H4

[0116] The dotted line graphs of the liquid products obtained in different waste residue ratios in Examples 6-11 are shown in Figure 4 As shown by Figure 4 It can be seen that the yield of liquid product reaches a peak value when raw material / waste residue = 1 / 3 as waste residue is added, and gradually decreases with continued addition.

[0117] The GC-MS furfural selectivity dotted line graphs of different waste residue ratios obtained in Examples 6-11 are shown in Figure 5 As shown by Figure 5 It can be seen that when the raw material / waste residue = 1 / 2.5, 1 / 3, the furfural selectivity is the highest.

[0118] The dotted line graph of GC combustible gas ratios of different waste residue ratios obtained in Examples 6-11 is shown in Figure 6 As shown by Figure 6 It can be seen that raw material / waste residue = 1 / 2.5, and combustible gas accounts for the largest proportion.

[0119] Example 12

[0120] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0121] (1) Dry the aquatic plant waste (lotus shell) and Al2O3-based waste platinum leaching residue in a 60°C drying oven for 18 h, and grind them through a 50-mesh sieve for later use.

[0122] (2) Take 5 g of the lotus shell biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 8 mm grinding tool and press the raw material by hot pressing. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0123] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 200 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0124] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 5 minutes, the solid products are collected.

[0125] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 64%. After GC-MS analysis, the furfural peak area in the liquid products reached 82%. After GC analysis of the gas products, the proportion of combustible gases reached 74%, including CO, H2, CH4, and C2H4.

[0126] Example 13

[0127] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0128] (1) Dry the aquatic plant waste (lotus shell) and Al2O3-based waste platinum leaching residue in a 60°C drying oven for 18 h, and grind them through a 50-mesh sieve for later use.

[0129] (2) Take 5 g of the lotus shell biomass raw material obtained in step (1) and 15 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 8 mm grinding tool and press the raw materials through a hot press. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0130] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 200 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0131] (4) The temperature of the tubular furnace is set to 400°C. After the temperature reaches 400°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 5 minutes, the solid products are collected.

[0132] After the catalytic pyrolysis experiment in the above process, the yield of liquid products is 60%. After GC-MS analysis, the furfural peak area in the liquid products can reach 80%. After GC analysis of the gas products, the combustible gas accounts for 70%, including CO, H2, CH4, and C2H4.

[0133] Embodiment 14

[0134] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0135] (1) Dry the aquatic plant waste (lotus leaves) and Al2O3-based waste platinum leaching residue in a drying oven at 60°C for 18 hours, and grind them through a 50-mesh sieve for later use.

[0136] (2) Take 5 g of the water lily biomass raw material obtained in step (1) and 12.5 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into an 8 mm grinding tool and press the raw material using a hot press. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0137] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and nitrogen is introduced into the quartz tube at a flow rate of 200 mL / min to ensure that the entire reaction stage is in an inert atmosphere.

[0138] (4) The temperature of the tubular furnace is set to 500°C. After the temperature reaches 500°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 5 minutes, the solid products are collected.

[0139] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 62%. After GC-MS analysis, the furfural peak area in the liquid products reached 83%. After GC analysis of the gas products, the proportion of combustible gases reached 76%, including CO, H2, CH4, and C2H4.

[0140] Embodiment 15

[0141] like Figure 1 As shown, the method for preparing highly selective furfural by catalytic pyrolysis of aquatic plant waste using Al2O3-based platinum leaching waste residue comprises the following specific steps:

[0142] (1) Dry the aquatic plant waste (lotus leaves) and Al2O3-based waste platinum leaching residue in a drying oven at 115°C for 24 hours, grind them through a 200-mesh sieve with a grinder and set them aside.

[0143] (2) Take 5 g of the lotus leaf biomass raw material obtained in step (1) and 20 g of Al2O3-based waste platinum leaching residue. After mixing evenly, put them into a 12 mm grinding tool and press the raw material using a hot press. The pressing strength during pressing is 7 MPa and the pressing time is 1 min.

[0144] (3) The pressed raw material obtained in step (2) is fixed in a quartz tube by quartz wool to ensure that it is in the constant temperature heating zone of the vertical tube furnace, and argon gas at a flow rate of 50 mL / min is introduced into the quartz tube to ensure that the entire reaction stage is in an inert atmosphere.

[0145] (4) The temperature of the tubular furnace is set to 800°C. After the temperature reaches 800°C, the quartz tube is placed in the tubular furnace for pyrolysis. The liquid and gas products produced by the pyrolysis are immediately collected. After the pyrolysis is completed for 30 minutes, the solid products are collected.

[0146] After the catalytic pyrolysis experiment in the above process, the yield of liquid products was 56%. After GC-MS analysis, the furfural peak area in the liquid products can reach 78%. After GC analysis of the gas products, the proportion of combustible gases reached 65%, including CO, H2, CH4, and C2H4.

[0147] In summary, the present invention dries the aquatic plant waste biomass (water hyacinth, lotus shell, lotus leaf) and waste residue separately, crushes and screens them, and then mixes them uniformly according to the mass ratio to obtain the pressed raw material; the pressed raw material is placed in the constant temperature heating zone of a vertical tube furnace for rapid catalytic pyrolysis at a temperature of 400-800°C, and pyrolyzes for 5-30 minutes in an inert atmosphere, and the aquatic plant waste produces solid-liquid-gas three-phase products under high-temperature catalytic pyrolysis; the volatile matter is condensed using an ice-water mixture to collect the pyrolysis oil with high furfural selectivity. The present invention utilizes the Pt metal active sites and acid sites with catalytic effects in the waste residue to catalyze the pyrolysis of aquatic plant waste biomass, and obtains a liquid phase product with up to 97% furfural selectivity and 95% combustible gas, and realizes the coordinated utilization of waste.

[0148] The above disclosure is only part of the embodiments of the present invention, which cannot be used to limit the scope of the present invention. Ordinary technicians in this field can understand that all or part of the processes of the above embodiments and equivalent changes made according to the claims of the present invention are still within the scope of the invention.

Claims

1. A method for preparing high-quality gas and liquid products by catalytic pyrolysis of aquatic plant waste by Al2O3-based platinum leaching waste residue, characterized in that: The steps include: The aquatic plant garbage and Al2O3-based platinum leaching waste residue are dried, crushed and sieved respectively to obtain aquatic plant garbage biomass powder and Al2O3-based platinum leaching waste residue powder for standby use; The aquatic plant waste biomass powder and the Al2O3-based platinum leaching waste residue powder are uniformly mixed to obtain a mixed powder; The mixed powder is pressed to obtain a pressed raw material; Under an inert atmosphere, the pressed raw material is rapidly pyrolyzed, and after the pyrolysis is completed, a non-condensable component and a condensable component are obtained; The condensable components are condensed to obtain bio-oil with high selectivity for furfural, and the non-condensable components are collected to obtain high-quality combustible synthesis gas.

2. The method for preparing high-quality bio-oil and synthesis gas by catalytic pyrolysis of aquatic plant waste biomass by Al2O3-based platinum leaching waste residue as claimed in claim 1, characterized in that: The aquatic plant garbage in step (1) is one or more of water hyacinth, lotus shell, lotus leaf or aquatic plant residue.

3. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that, The drying temperature in step (1) is 60-115°C, and the drying time is 12-24 hours; the sieving is through a 50-200 mesh sieve.

4. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that, In step (2), the mass ratio of the aquatic plant waste biomass powder to the Al2O3-based platinum leaching waste residue powder is 1:0.5~5.

5. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that, The pressing intensity during pressing in step (3) is 7 Mpa and the pressing time is 1 min.

6. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that: The diameter of the pressed raw material in step (3) is 8 to 12 mm.

7. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that: The pyrolysis temperature in step (4) is 400-800°C, and the pyrolysis time is 5-30 min.

8. The method for preparing furfural by catalytic pyrolysis of aquatic plant garbage by platinum leaching waste residue as claimed in claim 1, characterized in that: The inert atmosphere in step (4) is nitrogen or argon with a flow rate of 50-200 mL / min.

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