CN111876180A - Method for preparing nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxygenated biomass - Google Patents
Method for preparing nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxygenated biomass Download PDFInfo
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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- C07D209/04—Indoles; Hydrogenated indoles
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a method for preparing a nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxidized biomass, which mainly comprises the following steps: crushing and drying biomass, then carrying out biomass baking pretreatment in an ammonia atmosphere, and optimizing the element distribution of the biomass through deoxidation and nitrogen doping reaction so as to reduce the oxygen element content and improve the nitrogen element content in the biomass; and then mixing the nitrogen-doped deoxygenated biomass with a catalyst for catalytic pyrolysis to obtain a large amount of nitrogen-containing compounds with high added values, including pyridine compounds, pyrrole compounds, indole compounds and the like. According to the invention, the element distribution of the biomass is optimized through baking pretreatment, and the content of nitrogen-containing chemicals with high added value in the bio-oil is greatly promoted through ammonia baking pretreatment, modification and upgrading and then catalytic pyrolysis. And pyrolysis gas in the preparation process can be used as fuel, and the biochar after catalytic pyrolysis can be used in the fields of catalysis, energy storage, adsorption and the like. The method is beneficial to promoting the high-value utilization of the biomass waste.
Description
Technical Field
The invention relates to the field of biomass utilization, in particular to a method for preparing a nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxidized biomass.
Background
The nitrogenous chemical (pyrrole, pyridine, indole and the like) has the advantages of unique bioactivity, high systemic property, easy modification, low toxicity and the like, and is an intermediate platform compound which is urgently needed in the fine chemical fields of biomedicine, pesticide, dye and the like. The nitrogen heterocyclic ring-containing chemicals have extremely high market value and outstanding supply and demand contradiction, and are mainly prepared by direct extraction of non-renewable fossil fuel-based chemicals such as coal, petroleum and the like or secondary synthesis reaction of intermediate compounds at present. However, with the continuous exhaustion of fossil fuels and the problems of greenhouse gas emission and environmental pollution generated in the utilization process, the development of a production method and a process for preparing biomass-based nitrogen-containing heterocyclic chemicals by using renewable non-fossil fuel routes is urgent.
As a clean, renewable and abundant resource, compared with the traditional fossil fuel, the biomass fuel does not generate harmful substances and is an environment-friendly, clean and reliable green energy. Therefore, renewable biomass can be selected as a raw material to prepare the nitrogen-containing chemical through a catalytic pyrolysis technology. However, for nitrogen-containing chemicals (pyrrole, pyridine, and indole), biomass feedstocks lack available nitrogen and ineffective oxygen levels are too high to produce nitrogen-containing chemicals with higher nitrogen content if the biomass is subjected to conventional catalytic pyrolysis alone.
CN111363572A discloses a method for co-producing gas-liquid fuel, chemicals and carbon materials by catalytic pyrolysis of biomass, which is to perform catalytic pyrolysis on biomass to obtain volatile components rich in phenols and aromatic compounds. And carrying out on-line catalytic upgrading on the volatile matters to obtain phenol chemicals and aromatic hydrocarbon liquid fuel. And carrying out catalytic reforming on the uncondensed gas to obtain a methane-rich gas product. The biochar obtains the nitrogen-doped carbon material with developed porosity and rich active nitrogen-containing functional groups under the synergistic action of a low-proportion activating agent and ammonia gas. The aromatic hydrocarbon liquid fuel and the methane-rich gas fuel can be used for fuel cells, internal combustion engines and gas turbines to generate electricity and supply heat, and the nitrogen-doped carbon material can be used for catalysts, electrode materials and the like.
Disclosure of Invention
In view of the above defects and improvement requirements, the present invention aims to provide a method for preparing a nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxygenated biomass, so as to realize the preparation of the nitrogen-containing chemical product from biomass waste, improve the utilization value of the biomass waste, and alleviate the pressure caused by environmental pollution. The method has low cost and simple process, can efficiently prepare a large amount of liquid oil rich in nitrogen compounds, and greatly reduces the preparation cost of nitrogen-containing chemicals.
In order to achieve the above object, the present invention provides a method for preparing a nitrogen-containing chemical by catalytic pyrolysis of nitrogen-doped deoxygenated biomass, comprising the steps of:
(1) firstly, crushing biomass into powder, and then drying the powder;
(2) transferring the dried biomass powder into a quartz tube of a tube furnace, firstly introducing nitrogen or inert gas to blow the quartz tube to remove redundant air, then introducing ammonia, heating the tube furnace to a certain temperature after the ammonia gas flow is stable, and carrying out nitrogen-doped deoxidizing baking pretreatment to obtain nitrogen-doped deoxidizing biomass;
(3) after the baking pretreatment is finished, taking out the nitrogen-doped deoxidized biomass, uniformly mixing the nitrogen-doped deoxidized biomass with a catalyst according to the mass ratio of 1: 5-5: 1, then placing the mixture into a quartz tube, firstly introducing nitrogen or inert gas to sweep the quartz tube, removing redundant air, heating the quartz tube to a certain temperature by using a tube furnace after the gas flow is stable, and carrying out catalytic pyrolysis reaction to prepare the bio-oil rich in nitrogenous chemicals. The nitrogen-doped deoxidation roasting pretreatment process obviously improves the content of nitrogen elements in the biomass, reduces the content of oxygen elements, greatly improves the organic element distribution of the biomass, uses a catalyst in the catalytic pyrolysis process to further promote the generation of nitrogen-containing chemicals, and adopts a low-temperature condensation mode to cool the catalytic pyrolysis gas to obtain the bio-oil liquid rich in the nitrogen-containing chemicals.
(4) Extracting the biological oil liquid with an extractant, taking the extract, and performing rotary evaporation to obtain the nitrogen-containing chemical product.
Further, the biomass in the step (1) includes wood, moso bamboo, rice hull, corn straw, cotton stalk and other wood fiber materials, or any combination thereof.
Further, the ammonia gas flow in the step (2) is 100 mL/min-300 mL/min;
further, in the step (2), the temperature is raised to the nitrogen-doped deoxidation baking temperature of 200-300 ℃ at the temperature rise rate of 5-10 ℃/min, and the temperature is kept for 0.5-2.0 h;
further, the flow rate of the nitrogen or the inert gas in the step (3) is 150mL/min to 500 mL/min;
further, the temperature is increased to the catalytic pyrolysis temperature of 450-900 ℃ at the temperature increase rate of 10-40 ℃/min, and the temperature is maintained for 0.5-2.0 h.
Further, the catalyst in the step (3) is one or a combination of more of HY catalyst, ZSM-5 type molecular sieve, Beta molecular sieve, Y type molecular sieve, A type molecular sieve, MCM-41 molecular sieve, SAPO type molecular sieve and mordenite.
Further, in the step (4), the extracting agent is dichloromethane, ethanol, isopropanol or acetone, wherein the mass ratio of the biological oil to the extracting agent is 1: 1.
further, the nitrogen-containing compound obtained in the step (4) comprises pyridine compounds, pyrrole compounds, indole compounds and the like, wherein the pyrrole compounds comprise pyrrole, methyl pyrrole, 2-methyl pyrrole and the like; the pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, etc.; the indole compounds include indole, indoleacetic acid, and 2-methylindole.
The invention has the beneficial effects that:
according to the invention, the nitrogen-doped and oxygen-enriched biomass is pretreated by ammonia baking, so that the aim of nitrogen-doped and oxygen-enriched biomass is fulfilled, and then a proper catalyst is added for catalytic pyrolysis reaction, so that a nitrogen-containing chemical product with a high added value is obtained.
The baking carrier gas atmosphere has great influence on the baking and catalytic pyrolysis product characteristics, the common baking carrier gas atmosphere comprises inert gas, air, carbon dioxide, oxygen and the like, and different carrier gas atmospheres have respective advantages in baking. The ammonia atmosphere baking has the advantages that the ammonia atmosphere can chemically react with the biomass in the baking process, and nitrogen elements in the ammonia can be combined with components in the biomass, so that the nitrogen doping of the biomass is realized, and the content of the nitrogen elements is improved; secondly, oxygen in the biomass is removed in the form of gas components such as carbon monoxide, carbon dioxide and water in the baking process, so that the content of the oxygen is reduced.
The biomass catalytic pyrolysis technology can convert agricultural and forestry biomass such as bamboo wood into biochar and catalytic pyrolysis gas, the catalytic pyrolysis gas is condensed to obtain bio-oil liquid, part of non-condensable gas in the catalytic pyrolysis gas can be used as gas fuel (biofuel), and the bio-oil liquid is subjected to conventional extraction and rotary evaporation to obtain a nitrogen-containing chemical product. The obtained biochar has larger specific surface area and excellent electrochemical performance, and can be used in the fields of adsorption, catalysis, energy storage and the like. According to the method, biomass is used as a raw material, nitrogen-containing chemicals can be obtained after nitrogen-doping deoxidation baking and catalytic pyrolysis reaction, and a novel low-cost and easy-to-process method for preparing the nitrogen-containing chemicals is developed, so that high-valued utilization of biomass wastes is facilitated.
(1) In the method, the nitrogen-containing chemical product is prepared by a method of re-catalytic pyrolysis of nitrogen-doped deoxidizing baked biomass, and the biomass with different nitrogen element contents can be obtained by changing the nitrogen-doped deoxidizing baking temperature, specifically, after the moso bamboo is treated at the nitrogen-doped deoxidizing baking temperature of 300 ℃, the N element content is increased to 7.59% from 0.03%, and the O element content is reduced to 23.99% from 47.21%; after the nitrogen-doped deoxidation baking treatment at the temperature of 250 ℃, the content of N element is increased to 1.82% from 0.03%, and the content of O element is reduced to 42.25% from 47.21%; after the nitrogen-doped baking temperature is 210 ℃, the content of N element is increased to 1.40% from 0.03%, and the content of O element is reduced to 43.95% from 47.21%.
(2) After the biomass is subjected to nitrogen-doped deoxidation, baking and catalytic pyrolysis, condensing catalytic pyrolysis gas to obtain bio-oil rich in nitrogen-containing chemicals, specifically, nitrogen-containing compounds in the bio-oil obtained after condensing the catalytic pyrolysis gas generated by catalytic pyrolysis of moso bamboo mainly comprise pyridine, pyrrole, indole and the like, wherein the pyrrole compounds comprise pyrrole, methyl pyrrole, 2-methyl pyrrole and the like; the pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, etc.; the indole compounds include indole, indoleacetic acid, and 2-methylindole. The method of the invention realizes the continuous and efficient preparation of the nitrogen-containing chemical, simplifies the process steps of the preparation of the nitrogen-containing chemical, reduces the difficulty of operation, prepares biomass as raw materials and greatly reduces the preparation cost of the nitrogen-containing chemical. The method realizes high-value utilization of the biomass waste.
(3) The biochar obtained by the method has larger specific surface area, higher nitrogen content, lower oxygen content and rich active nitrogen-containing functional groups, and can be used in the fields of adsorption, catalysis, energy storage and the like.
(4) Part of the uncondensable catalytic pyrolysis gas obtained in the method can be used as fuel gas for combustion, so that the utilization efficiency of the biomass is improved.
(5) The invention patent and CN111363572A have obvious difference in process and effect, and the process is as follows: the baking atmosphere of the invention is ammonia gas, while the baking atmosphere of CN111363572A is nitrogen gas or argon gas; the catalyst is one or a combination of more of HY catalyst, ZSM-5 type molecular sieve, Beta molecular sieve, Y type molecular sieve, A type molecular sieve, MCM-41 molecular sieve, SAPO type molecular sieve and mordenite, and the CN111363572A catalyst is Ni/Fe loaded porous nitrogen-doped carbon catalyst or Ni/Co loaded porous nitrogen-doped carbon catalyst; the liquid product of the invention is obtained by extraction, and the liquid product is not extracted in the method described in CN 111363572A. In effect: the invention aims to obtain nitrogen-containing chemicals, and CN111363572A liquid products mainly comprise phenolic chemicals and aromatic hydrocarbon liquid fuels.
Drawings
FIG. 1 is a flow chart of a process for preparing a nitrogen-containing chemical by catalytic pyrolysis of nitrogen-doped deoxygenated biomass;
FIG. 2 is a GC-MS spectrum of a nitrogen-containing chemical prepared in example 1 of the present invention;
FIG. 3 is a GC-MS spectrum of a nitrogen-containing chemical prepared in example 2 of the present invention;
FIG. 4 is a GC-MS spectrum of a nitrogen-containing chemical prepared in example 3 of the present invention;
FIG. 5 is a GC-MS spectrum of a nitrogen-containing chemical prepared in example 4 of the present invention;
FIG. 6 is a GC-MS spectrum of a nitrogen-containing chemical prepared in example 5 of the present invention;
Detailed Description
The present invention will be specifically described below with reference to examples.
Example 1
Pulverizing moso bamboo into 200 mesh powder, and drying in oven at 105 deg.C for 24 hr; uniformly paving 2g of dried moso bamboo powder on a crucible, immediately transferring the crucible to a quartz tube of a tube furnace, firstly introducing nitrogen or inert gas to blow the quartz tube to remove redundant air, then introducing ammonia, heating the tube furnace to a certain temperature after the ammonia gas flow is stable, and carrying out nitrogen-doped deoxidizing baking pretreatment to obtain the nitrogen-doped deoxidizing biomass. In the pre-treatment process of nitrogen-doping deoxidation baking, the flow of ammonia gas is 100mL/min, the fixed heating rate is 10 ℃/min, and after heating to 300 ℃, the temperature is kept for 30 min. And after the nitrogen-doped deoxidation baking process is finished, closing ammonia gas, fully mixing the nitrogen-doped deoxidation biomass and the HY catalyst according to the mass ratio of 3:1, then placing the mixture into a quartz tube of a tube furnace, introducing nitrogen gas for a certain time, and starting to perform catalytic pyrolysis reaction. In the catalytic pyrolysis process, the nitrogen flow is 300mL/min, the fixed heating rate is 10 ℃/min, and the temperature is kept for 60min after the temperature is heated to 900 ℃. Cooling the catalytic pyrolysis gas in a condensation mode to obtain the biological oil liquid rich in nitrogen-containing chemicals. Extracting the bio-oil liquid with ethanol (the mass ratio of the bio-oil to the ethanol is 1: 1), taking the extract, and carrying out rotary evaporation to obtain a nitrogen-containing chemical liquid product rich in nitrogen-containing compounds. Through detection, the content of N element in the moso bamboo subjected to nitrogen-doped baking pretreatment is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and nitrogen-containing compounds in the collected liquid product mainly comprise pyridine compounds, pyrrole compounds, indole compounds and the like. The yield of the nitrogen-containing compound reaches 19.89 percent. Wherein the selectivity of 2-methylpyrrole reaches 15%, the selectivity of 2-methylpyridine reaches 29%, and the selectivity of 2-methylindole reaches 21%.
Example 2
This example is the same as example 1 except that the catalytic pyrolysis temperature is 500 ℃. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 42.25%, and the yield of the obtained nitrogen-containing compound is 15.84%. Wherein the selectivity of 2-methylpyrrole reaches 19%, the selectivity of 2-methylpyridine reaches 37%, and the selectivity of 2-methylindole reaches 16%.
Example 3
This example is the same as example 1 except that the baking temperature is 250 ℃. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 1.82%, the content of O element is reduced from 47.21% to 43.95%, and the yield of the obtained nitrogen-containing compound is 10.70%. Wherein the selectivity of 2-methylpyrrole reaches 24%, the selectivity of 2-methylpyridine reaches 35%, and the selectivity of 2-methylindole reaches 41%.
Example 4
This example is the same as example 1 except that the baking temperature is 250 ℃ and the catalytic pyrolysis temperature is 750 ℃. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 1.40%, the content of O element is reduced from 47.21% to 43.95%, and the yield of the obtained nitrogen-containing compound is 10.02%. Wherein the selectivity of 2-methylpyrrole reaches 23%, the selectivity of 2-methylpyridine reaches 39%, and the selectivity of 2-methylindole reaches 38%.
Example 5
This example is the same as example 1 except that the baking temperature is 250 ℃ and the catalytic pyrolysis temperature is 550 ℃. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 43.95%, and the yield of the obtained nitrogen-containing compound is 9.56%. Wherein the selectivity of 2-methylpyrrole reaches 17%, the selectivity of 2-methylpyridine reaches 33%, and the selectivity of 2-methylindole reaches 29%.
Example 6
This example is the same as example 3 except that the starting material is rice hulls. Through detection, the content of N element in the rice hulls subjected to nitrogen-doped deoxidizing baking pretreatment is increased from 1.2% to 6.39%, the content of O element is reduced from 55.72% to 29.33%, and the yield of the obtained nitrogen-containing compound is 13.26%. Wherein the selectivity of 2-methylpyrrole reaches 27%, the selectivity of 2-methylpyridine reaches 18%, and the selectivity of 2-methylindole reaches 24%.
Example 7
This example is the same as example 4 except that the raw material was cornstalks. Through detection, the content of N element in the corn stalks pretreated by nitrogen-doped deoxidation roasting is increased from 0.64% to 4.49%, the content of O element is reduced from 49.63% to 28.46%, and the yield of the obtained nitrogen-containing compound is 11.26%. Wherein the selectivity of 2-methylpyrrole reaches 13%, the selectivity of 2-methylpyridine reaches 28%, and the selectivity of 2-methylindole reaches 15%.
Example 8
This example is the same as example 5 except that the raw material is cotton stalk. Through detection, the content of N element in the cotton stalk pretreated by nitrogen-doped deoxidation baking is increased from 0.78% to 4.69%, the content of O element is reduced from 54.19% to 32.18%, and the yield of the obtained nitrogen-containing compound is 8.89%. Wherein the selectivity of 2-methylpyrrole reaches 12%, the selectivity of 2-methylpyridine reaches 18%, and the selectivity of 2-methylindole reaches 25%.
Example 9
This example is the same as example 1 except that the raw material is poplar. Through detection, the content of N element in the poplar wood pretreated by nitrogen-doped deoxidation baking is increased from 0.56% to 7.98%, the content of O element is reduced from 43.79% to 20.21%, and the yield of the obtained nitrogen-containing compound is 18.65%. Wherein the selectivity of 2-methylpyrrole reaches 21%, the selectivity of 2-methylpyridine reaches 23%, and the selectivity of 2-methylindole reaches 19%.
Example 10
This example is the same as example 1 except that the mass ratio of the nitrogen-doped deoxygenated biomass to the catalyst is 1: 5. through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and the yield of the obtained nitrogen-containing compound is 15.05%. Wherein the selectivity of 2-methylpyrrole reaches 14%, the selectivity of 2-methylpyridine reaches 23%, and the selectivity of 2-methylindole reaches 25%.
Example 11
This example is the same as example 8 except that the baking soak time was 2 hours. Through detection, the content of N element in the cotton stalk pretreated by nitrogen-doped deoxidation baking is increased from 0.78% to 6.93%, the content of O element is reduced from 54.19% to 24.12%, and the yield of the obtained nitrogen-containing compound is 14.17%. Wherein the selectivity of 2-methylpyrrole reaches 19%, the selectivity of 2-methylpyridine reaches 23%, and the selectivity of 2-methylindole reaches 27%.
Example 12
This example is the same as example 8 except that the ammonia flow rate during the baking process was 300 mL/min. Through detection, the content of N element in the cotton stalk pretreated by nitrogen-doped deoxidation baking is increased from 0.78% to 6.53%, the content of O element is reduced from 54.19% to 28.43%, and the yield of the obtained nitrogen-containing compound is 12.17%. Wherein the selectivity of 2-methylpyrrole reaches 19%, the selectivity of 2-methylpyridine reaches 23%, and the selectivity of 2-methylindole reaches 29%.
Example 13
This example is the same as example 1 except that the heating rate during pyrolysis was 40 ℃/min and the pyrolysis hold time was 0.5 h. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and the yield of the obtained nitrogen-containing compound is 14.78%. Wherein the selectivity of 2-methylpyrrole reaches 17%, the selectivity of 2-methylpyridine reaches 31%, and the selectivity of 2-methylindole reaches 25%.
Example 14
This example is the same as example 13, except that the pyrolysis hold time is 2 h. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and the yield of the obtained nitrogen-containing compound is 17.33%. Wherein the selectivity of 2-methylpyrrole reaches 18%, the selectivity of 2-methylpyridine reaches 31%, and the selectivity of 2-methylindole reaches 23%.
Example 15
This example is the same as example 1 except that the nitrogen flow during pyrolysis was 150 mL/min. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and the yield of the obtained nitrogen-containing compound is 16.58%. Wherein the selectivity of 2-methylpyrrole reaches 16%, the selectivity of 2-methylpyridine reaches 27%, and the selectivity of 2-methylindole reaches 24%.
Example 16
This example is the same as example 1 except that the nitrogen flow during pyrolysis was 500 mL/min. Through detection, the content of N element in the moso bamboo pretreated by nitrogen-doped deoxidation baking is increased from 0.03% to 7.59%, the content of O element is reduced from 47.21% to 23.99%, and the yield of the obtained nitrogen-containing compound is 16.99%. Wherein the selectivity of 2-methylpyrrole reaches 18%, the selectivity of 2-methylpyridine reaches 25%, and the selectivity of 2-methylindole reaches 23%.
Example 17
In this example, the effect of ammonia atmosphere baking on the phyllostachys pubescens element, calorific value, quality and energy yield was studied. Table 1 shows that the ammonia atmosphere nitrogen-doped deoxidation baking of the moso bamboo has obvious effects on introducing an external nitrogen source and removing oxygen elements.
TABLE 1 influence of nitrogen-doped deoxidation baking in ammonia atmosphere on Phyllostachys pubescens element, calorific value, quality and energy yield
The reaction process is as follows: pulverizing moso bamboo into 200 mesh powder, and drying in oven at 105 deg.C for 24 hr; uniformly paving dried moso bamboo powder with a certain mass (the mass of unbaked raw materials) on a crucible, immediately transferring the moso bamboo powder into a quartz tube of a tube furnace, firstly introducing nitrogen or inert gas to sweep the quartz tube, removing redundant air, then introducing ammonia gas, wherein the flow rate of the ammonia gas is 100mL/min, fixing the heating rate at 10 ℃/min after the ammonia gas flow is stable, heating the tube furnace to different baking temperatures in the table 1, baking and keeping the temperature for 30min, and carrying out nitrogen-doped deoxidation baking pretreatment to obtain the nitrogen-doped deoxidation biomass.
The mass yield is the percentage of the mass of the nitrogen-doped deoxidized biomass to the mass of the unbaked raw material.
The percentages of the elements in table 1 refer to the mass percentages of the corresponding elements in the nitrogen-doped deoxygenated biomass and unbaked feedstock.
The higher heating value in table 1 refers to the total heat evolved by complete combustion of the fuel, including the heat of condensation of the generated water vapor.
The energy yield in table 1 refers to the ratio of the total calorific value of the raw material after baking to the total calorific value before baking.
Example 18
In this example, the effect of different pyrolysis temperatures on the yield and selectivity of nitrogen-containing compounds was investigated. Table 2 shows that the yield of nitrogen-containing compounds increases with increasing temperature.
TABLE 2 influence of pyrolysis temperature on yield and selectivity of nitrogen-containing compounds
The reaction conditions are that the reaction raw material is moso bamboo, ammonia flow is 100mL/min in the nitrogen-doped deoxidation baking process, the fixed heating rate is 10 ℃/min, the baking temperature is 300 ℃, and the baking heat preservation time is 30 min; the mass ratio of the nitrogen-doped deoxygenated biomass to the HY catalyst is 3: 1; in the pyrolysis process, the flow rate of nitrogen gas is 300mL/min, the fixed heating rate is 10 ℃/min, the pyrolysis heat preservation time is 60min, and the extracting agent is ethanol.
The carbon conversion rate of liquid, gas and solid refers to the proportion of carbon in the raw material converted into carbon in each product, namely the ratio of the carbon content in each product to the carbon content in the raw material.
The carbon yield of the nitrogen-containing compound means the ratio of the carbon content in the nitrogen-containing compound to the carbon content in the raw material.
The selective yield of nitrogen-containing compounds in the liquid product refers to the ratio of the total mass of nitrogen-containing compounds in the liquid product to the total mass of the liquid product.
Example 19
In this example, the effect of different extractants on nitrogen-containing compound yield and selectivity was investigated.
TABLE 3 influence of the extractant on the yield and selectivity of the nitrogenous compound
The reaction conditions are that the reaction raw material is moso bamboo, ammonia flow is 100mL/min in the nitrogen-doped deoxidation baking process, the fixed heating rate is 10 ℃/min, the baking temperature is 300 ℃, and the baking heat preservation time is 30 min; the mass ratio of the nitrogen-doped deoxygenated biomass to the HY catalyst is 3: 1; in the pyrolysis process, the flow rate of nitrogen gas is 300mL/min, the fixed heating rate is 10 ℃/min, the pyrolysis heat preservation time is 60min, and the pyrolysis temperature is 900 ℃.
Example 20
In this example, the effect of different catalysts on the yield and selectivity of nitrogen-containing compounds was investigated.
TABLE 4 influence of different catalysts on the yield and selectivity of nitrogen-containing compounds
The reaction conditions are that the reaction raw material is moso bamboo, ammonia flow is 100mL/min in the baking process, the fixed heating rate is 10 ℃/min, the baking temperature is 300 ℃, and the baking heat preservation time is 30 min; the mass ratio of the nitrogen-doped deoxygenated biomass to the different catalysts in table 3 was 3: 1; in the pyrolysis process, the flow rate of nitrogen gas is 300mL/min, the fixed heating rate is 10 ℃/min, the pyrolysis heat preservation time is 60min, the pyrolysis temperature is 800 ℃, and the extracting agent is ethanol.
The invention discloses a method for preparing a nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxidized biomass, which mainly comprises the following steps: crushing and drying biomass, then carrying out a biomass baking pretreatment process in an ammonia atmosphere, and optimizing the element distribution of the biomass through deoxidation and nitrogen doping reaction, so that the content of oxygen elements in the biomass is obviously reduced, and the content of nitrogen elements in the biomass is obviously improved; and then uniformly mixing the nitrogen-doped deoxygenated biomass and a catalyst for catalytic pyrolysis to obtain a large amount of nitrogen-containing compounds with high added values, including pyridine compounds, pyrrole compounds, indole compounds and the like. In the process of preparing the nitrogen-containing chemical product by catalytic pyrolysis of the nitrogen-doped deoxidized biomass, the invention optimizes the element distribution of the biomass, and greatly promotes the content of the nitrogen-containing chemical product with high added value in the bio-oil by ammonia baking pretreatment, modification and upgrading and then catalytic pyrolysis. And pyrolysis gas in the preparation process can be used as fuel, and the biochar after catalytic pyrolysis can be used in the fields of catalysis, energy storage, adsorption and the like. The method is beneficial to promoting the high-value utilization of the biomass waste.
Claims (9)
1. A method for preparing a nitrogen-containing chemical product by catalytic pyrolysis of nitrogen-doped deoxygenated biomass is characterized by comprising the following steps of:
(1) firstly, crushing biomass into powder, and then drying the powder;
(2) transferring the dried biomass powder into a quartz tube of a tube furnace, firstly introducing nitrogen or inert gas to blow the quartz tube to remove redundant air, then introducing ammonia, heating the tube furnace to a certain temperature after the ammonia gas flow is stable, and carrying out nitrogen-doped deoxidizing baking pretreatment to obtain nitrogen-doped deoxidizing biomass;
(3) after the baking pretreatment is finished, taking out the nitrogen-doped deoxidized biomass, uniformly mixing the nitrogen-doped deoxidized biomass with a catalyst according to the mass ratio of 1: 5-5: 1, then placing the mixture into a quartz tube, firstly introducing nitrogen or inert gas to sweep the quartz tube, removing redundant air, heating the quartz tube to a certain temperature by using a tube furnace after the gas flow is stable, and carrying out catalytic pyrolysis reaction to prepare bio-oil rich in nitrogenous chemicals;
(4) extracting the biological oil liquid with an extractant, taking the extract, and performing rotary evaporation to obtain the nitrogen-containing chemical product.
2. The method for preparing nitrogen-containing chemicals through catalytic pyrolysis of nitrogen-doped deoxygenated biomass according to claim 1, wherein the biomass in step (1) comprises wood, moso bamboo, rice hulls, corn stover, cotton stalks, or any combination thereof.
3. The method for preparing the nitrogen-containing chemical product by catalytic pyrolysis of the nitrogen-doped deoxygenated biomass according to claim 1, wherein the ammonia gas flow in the step (2) is 100-300 mL/min.
4. The method for preparing the nitrogen-containing chemical product by the catalytic pyrolysis of the nitrogen-doped deoxidized biomass according to claim 1, wherein in the step (2), the temperature is raised to the nitrogen-doped deoxidized baking temperature of 200-300 ℃ at the temperature-raising rate of 5-10 ℃/min, and the temperature is kept for 0.5-2.0 h.
5. The method for preparing nitrogen-containing chemicals by catalytic pyrolysis of nitrogen-doped deoxygenated biomass according to claim 1, wherein the flow rate of nitrogen or inert gas in step (3) is 150-500 mL/min.
6. The method for preparing the nitrogen-containing chemical product by the catalytic pyrolysis of the nitrogen-doped deoxidized biomass as claimed in claim 1, wherein in the step (3), the temperature is raised to the catalytic pyrolysis temperature of 450-900 ℃ at the temperature raising rate of 10-40 ℃/min, and the temperature is maintained for 0.5-2.0 h.
7. The method for preparing nitrogen-containing chemicals by catalytic pyrolysis of nitrogen-doped deoxidized biomass according to claim 1, wherein in the step (3), the catalyst is one or more of HY catalyst, ZSM-5 type molecular sieve, Beta molecular sieve, Y type molecular sieve, A type molecular sieve, MCM-41 molecular sieve, SAPO type molecular sieve and mordenite.
8. The method for preparing nitrogen-containing chemicals through catalytic pyrolysis of nitrogen-doped deoxygenated biomass according to claim 1, wherein the extracting agent in the step (4) is dichloromethane, ethanol, isopropanol or acetone, and the mass ratio of the bio-oil to the extracting agent is 1: 1.
9. the method for preparing nitrogen-containing chemicals by catalytic pyrolysis of nitrogen-doped deoxygenated biomass according to claim 1, wherein the nitrogen-containing chemicals obtained in step (4) comprise pyrrole compounds, pyridine compounds and indole compounds; wherein the pyrrole compounds comprise pyrrole, methyl pyrrole and 2-methyl pyrrole; the pyridine compounds include pyridine, 2-methylpyridine and 3-methylpyridine; the indole compounds include indole, indoleacetic acid, and 2-methylindole.
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| CN112831330A (en) * | 2020-12-31 | 2021-05-25 | 西北农林科技大学 | Method for co-producing ammoniated biomass charcoal, ammoniated bio-oil and ammonium salt by ammoniated pyrolysis of biomass and product application |
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