CN113999691B - Process for preparing hydrogen oil by high-temperature conversion of garbage - Google Patents
Process for preparing hydrogen oil by high-temperature conversion of garbage Download PDFInfo
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- CN113999691B CN113999691B CN202111487511.7A CN202111487511A CN113999691B CN 113999691 B CN113999691 B CN 113999691B CN 202111487511 A CN202111487511 A CN 202111487511A CN 113999691 B CN113999691 B CN 113999691B
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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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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Abstract
The invention discloses a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps: s1, screening out biomass garbage in garbage, adding phosphite and water into the biomass garbage, mixing and heating to 70-80 ℃; carrying out high-temperature heating decomposition on the heated mixture to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance and a first liquid decomposed substance, and S2, pretreating the first solid decomposed substance to obtain a hydrogenation catalyst; s3, carrying out hydrogenation reaction on the first liquid decomposer and a hydrogenation catalyst to obtain a first reactant, S4, hydrogenating the first reactant and the hydrogenation catalyst to obtain a second reactant, and separating to obtain an oily substance, namely the hydrogen oil. The process for preparing the hydrogen oil by the high-temperature garbage biomass provided by the invention is simple in whole process, easy to operate and widely applicable. In addition, the first solid decomposition product generated in the process is used for preparing the hydrogenation catalyst, so that the catalytic effect is good, and the cost is saved.
Description
Technical Field
The invention relates to the field of hydrogen oil preparation by garbage high-temperature conversion. More specifically, the invention relates to a process for preparing hydrogen oil by high-temperature garbage conversion.
Background
At present, chinese is pushing forward garbage classification, and actually the garbage classification is just the early stage of garbage treatment, and how to change garbage into valuables is the final aim. The daily domestic garbage of China is about 4 hundred million tons (data published in 2018) every year, and at the present stage, garbage treatment has two modes, namely landfill and incineration, wherein the landfill pollutes soil, underground water, environment and the like, and a large amount of beneficial substances are lost during incineration.
Disclosure of Invention
To achieve these objects and other advantages in accordance with the present invention, there is provided a process for preparing hydrogen oil by high-temperature reforming of garbage, comprising the steps of:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 50-70%, and the w/w concentration of the phosphite is 0.3-1.8%; heating the mixed mixture to 70-80 ℃, preserving heat for 4 hours, and keeping the stirring state in the heating and heat preserving process;
carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance comprising semi-coke and a first liquid decomposed substance comprising pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
s3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
Preferably, the process for preparing hydrogen oil by high-temperature garbage conversion, in which the first solid decomposition product obtained in step S2 is pretreated to obtain a hydrogenation catalyst, specifically includes the following steps:
preheating the first solid decomposer in a muffle furnace to 180-210 ℃, and keeping the temperature for 15-30 min; heating to 350-450 ℃, keeping the temperature for 120-135 min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, adjusting the pH value of the silica gel solution to 3-4 by using acid liquor, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar weight of the sodium carbonate is not less than the sum of the added molar weights of the copper nitrate and the strontium nitrate;
and after stirring, standing for 12-14 h, washing with water until the pH of washing liquor is close to 7, vacuum drying, roasting in a muffle furnace, and finally introducing hydrogen for reduction reaction.
Preferably, in the process for preparing hydrogen oil by high-temperature garbage conversion, in step S1, the step of heating the mixed mixture to 70-80 ℃, specifically includes:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
finally, naturally cooling to 70-80 ℃.
Preferably, in the process for preparing hydrogen oil by high-temperature conversion of the garbage, the w/w concentration of the biomass garbage is 64%, and the w/w concentration of phosphite is 1.2%.
Preferably, in the process for preparing the hydrogen oil by high-temperature conversion of the garbage, the acid solution is a nitric acid solution.
Preferably, in the process for preparing hydrogen oil by high-temperature garbage conversion, the molar amount of sodium carbonate added is slightly larger than the sum of the molar amounts of copper nitrate and strontium nitrate.
Preferably, in the process for preparing hydrogen oil by high-temperature garbage conversion, hydrogen is introduced for reduction reaction, and the hydrogen is introduced until the temperature naturally reaches room temperature after the reduction reaction is finished, so that the hydrogen can be stopped from being introduced.
Preferably, in the process for preparing the hydrogen oil by high-temperature garbage conversion, hydrogen is introduced for reduction reaction, and the reaction temperature is 200-280 ℃.
The invention at least comprises the following beneficial effects: the process for preparing hydrogen oil from high-temperature garbage biomass comprises the steps of pretreating the biomass garbage by using phosphite, heating and stirring, carrying out micro-activation treatment on the biomass by using the phosphite, opening micro-channels on the surface of the biomass garbage, carrying out high-temperature heating decomposition treatment on the biomass garbage after being treated by using a high-temperature decomposition tower, and carrying out secondary hydrogenation treatment by using a hydrogenation catalyst prepared from a first solid decomposer, wherein the secondary hydrogenation effect is better compared with that of primary hydrogenation, the primary hydrogenation can be carried out in the secondary hydrogenation, and the material which is not hydrogenated in the primary hydrogenation can be further hydrogenated by using the hydrogen added in the second hydrogenation, so that the full coverage of 100% of the hydrogenation can be ensured, and the target product hydrogen oil can be obtained. In addition, the first solid decomposition product generated in the process is used for preparing the hydrogenation catalyst, so that the catalytic effect is good, and the cost is saved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
Example 1
The invention relates to a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 50%, and the w/w concentration of the phosphite is 0.3%; heating the mixed mixture to 70 ℃, preserving heat for 4 hours, and keeping the stirring state in the heating and heat preserving process;
wherein, the mixed mixture is heated to 70 ℃ again, and the method specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
and finally, naturally cooling to 70 ℃.
Carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance comprising semi-coke and a first liquid decomposed substance comprising pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
the method for pretreating the first solid decomposition product obtained in the step S2 to obtain the hydrogenation catalyst specifically comprises the following steps:
preheating the first solid decomposition product in a muffle furnace to 180 ℃, and keeping the temperature for 15min; heating to 350 ℃, keeping the temperature for 120min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, adjusting the pH of the silica gel solution to 3 by using a nitric acid solution, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar quantity of the sodium carbonate is slightly larger than the sum of the added molar quantities of the copper nitrate and the strontium nitrate;
and after stirring, standing for 12h, washing with water until the pH of washing liquor is close to 7, drying in vacuum, roasting in a muffle furnace, and finally introducing hydrogen to carry out reduction reaction to obtain the hydrogenation catalyst, wherein the reaction temperature is 200 ℃. After the reduction reaction is finished, introducing hydrogen until the temperature naturally reaches the room temperature, and stopping introducing the hydrogen.
S3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
The process for preparing hydrogen oil from high-temperature garbage biomass comprises the steps of pretreating the biomass garbage by using phosphite, heating and stirring, carrying out micro-activation treatment on the biomass by using the phosphite, opening micro-channels on the surface of the biomass garbage, carrying out high-temperature heating decomposition treatment on the biomass garbage after the treatment by using a high-temperature decomposition tower, and carrying out secondary hydrogenation treatment by using a hydrogenation catalyst prepared from a first solid decomposition product, wherein the secondary hydrogenation effect is better compared with that of primary hydrogenation, the primary hydrogenation can be carried out in the secondary hydrogenation, and the material which is not hydrogenated in the primary hydrogenation can be further hydrogenated by the secondary hydrogenation, so that the hydrogen oil which is a target product can be obtained by ensuring 100% full coverage of hydrogenation. In addition, the first solid decomposition product generated in the process is used for preparing the hydrogenation catalyst, so that the catalytic effect is good, and the cost is saved.
Example 2
The invention relates to a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 64%, and the w/w concentration of the phosphite is 1.2%; heating the mixed mixture to 75 ℃, preserving the heat for 4 hours, and keeping the stirring state in the heating and heat preserving process;
wherein, the mixed mixture is heated to 75 ℃ again, and the method specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
and finally, naturally cooling to 75 ℃.
Carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance containing semi-coke and a first liquid decomposed substance containing pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
the method for pretreating the first solid decomposition product obtained in the step S2 to obtain the hydrogenation catalyst specifically comprises the following steps:
preheating the first solid decomposition product in a muffle furnace to 190 ℃, and keeping the temperature for 24min; heating to 400 ℃, preserving heat for 128min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, regulating the pH value of the silica gel solution to 3.5 by using a nitric acid solution, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar amount of the sodium carbonate is slightly larger than the sum of the added molar amounts of the copper nitrate and the strontium nitrate;
and after stirring, standing for 13h, washing with water until the pH of washing liquor is close to 7, drying in vacuum, roasting in a muffle furnace, and finally introducing hydrogen to carry out reduction reaction to obtain the hydrogenation catalyst, wherein the reaction temperature is 250 ℃. After the reduction reaction is finished, introducing hydrogen until the temperature naturally reaches the room temperature, and stopping introducing the hydrogen.
S3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
Example 3
The invention relates to a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 70%, and the w/w concentration of the phosphite is 1.8%; heating the mixed mixture to 80 ℃, preserving heat for 4 hours, and keeping the stirring state in the heating and heat preserving process;
wherein, the mixed mixture is heated to 80 ℃ and the method specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
and finally naturally cooling to 80 ℃.
Carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance containing semi-coke and a first liquid decomposed substance containing pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
the method for pretreating the first solid decomposition product obtained in the step S2 to obtain the hydrogenation catalyst specifically comprises the following steps:
preheating the first solid decomposer in a muffle furnace to 210 ℃, and keeping the temperature for 30min; heating to 450 ℃, preserving heat for 135min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, adjusting the pH of the silica gel solution to 4 by using a nitric acid solution, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar amount of the sodium carbonate is slightly larger than the sum of the added molar amounts of the copper nitrate and the strontium nitrate;
and after stirring, standing for 14h, washing with water until the pH of washing liquor is close to 7, drying in vacuum, roasting in a muffle furnace, and finally introducing hydrogen to carry out reduction reaction to obtain the hydrogenation catalyst, wherein the reaction temperature is 280 ℃. After the reduction reaction is finished, introducing hydrogen until the temperature naturally reaches the room temperature, and stopping introducing the hydrogen.
S3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
Comparative example 1
The invention relates to a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 51%, and the w/w concentration of the phosphite is 0.02%; heating the mixed mixture to 50 ℃, preserving heat for 3 hours, and keeping the stirring state in the heating and heat preserving process;
wherein, the mixed mixture is heated to 50 ℃ again, and the method specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
and finally, naturally cooling to 50 ℃.
Carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance containing semi-coke and a first liquid decomposed substance containing pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
the method for pretreating the first solid decomposition product obtained in the step S2 to obtain the hydrogenation catalyst specifically comprises the following steps:
preheating the first solid decomposition product in a muffle furnace to 210 ℃, and preserving the temperature for 30min; heating to 450 ℃, preserving heat for 135min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, adjusting the pH of the silica gel solution to 4 by using a nitric acid solution, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar quantity of the sodium carbonate is slightly larger than the sum of the added molar quantities of the copper nitrate and the strontium nitrate;
and after stirring, standing for 14h, washing with water until the pH of washing liquor is close to 7, drying in vacuum, roasting in a muffle furnace, and finally introducing hydrogen to carry out reduction reaction at the reaction temperature of 280 ℃. After the reduction reaction is finished, introducing hydrogen until the temperature naturally reaches the room temperature, and stopping introducing the hydrogen.
S3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
Comparative example 2
The invention relates to a process for preparing hydrogen oil by garbage high-temperature conversion, which comprises the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 70%, and the w/w concentration of the phosphite is 1.8%; heating the mixed mixture to 80 ℃, preserving heat for 4 hours, and keeping the stirring state in the heating and heat preserving process;
wherein, the mixed mixture is heated to 80 ℃, and the method specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
and finally naturally cooling to 80 ℃.
Carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance comprising semi-coke and a first liquid decomposed substance comprising pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, directly purchasing a hydrogenation catalyst on the market;
s3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
and S4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil.
TABLE 1 conversion of the products (mass ratio of hydrogen oil/Biomass refuse) of the examples
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Conversion rate | 49％ | 54％ | 51％ | 24％ | 18％ |
From the above data, it can be seen that the hydrogen-oil ratio obtained by the production processes of examples 1 to 3 is higher than that obtained by comparative example 1 in which the above-specified range is exceeded and comparative example 2 in which the produced hydrogenation catalyst is not used, and it is confirmed that the above-described excellent effects can be obtained by using the hydrogenation catalyst produced in the present application at the above-described ratio.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, particular embodiments, but rather to those skilled in the art, and it is to be understood that the invention is capable of numerous modifications and that various changes may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (7)
1. A process for preparing hydrogen oil by garbage high-temperature conversion is characterized by comprising the following steps:
s1, screening out biomass garbage in the garbage, adding phosphite and water into the biomass garbage, and mixing, wherein the w/w concentration of the biomass garbage is 50-70%, and the w/w concentration of the phosphite is 0.3-1.8%; heating the mixed mixture to 70-80 ℃, preserving heat for 4h, and keeping the stirring state in the heating and heat preserving process;
carrying out high-temperature heating decomposition on the heated mixture in a high-temperature decomposition tower to obtain a first decomposed substance, separating the first decomposed substance to obtain a first solid decomposed substance containing semi-coke and a first liquid decomposed substance containing pyrolysis water and biological tar, and separating decomposed gas generated in the process from the high-temperature decomposition tower;
s2, pretreating the first solid decomposition product obtained in the step S1 to obtain a hydrogenation catalyst;
s3, placing the first liquid decomposition product obtained in the step S1 and the hydrogenation catalyst obtained in the step S2 into a hydrogenation reactor for hydrogenation reaction to obtain a first reactant,
s4, carrying out further hydrogenation reaction on the first reactant obtained in the step S3 and the hydrogenation catalyst obtained in the step S2 on a fixed bed to obtain a second reactant, carrying out distillation reaction, and separating to obtain an oily substance, namely the target product hydrogen oil;
the method for pretreating the first solid decomposition product obtained in the step S2 to obtain the hydrogenation catalyst specifically comprises the following steps:
preheating the first solid decomposer in a muffle furnace to 180-210 ℃, and keeping the temperature for 15-30 min; heating to 350-450 ℃, keeping the temperature for 120-135 min, cooling to room temperature to obtain carbide, grinding the carbide into powder, adding the powder into a silica gel solution, adjusting the pH value of the silica gel solution to 3-4 by using acid liquor, dropwise adding a copper nitrate solution and a strontium nitrate solution into the silica gel solution, and continuously stirring;
continuously adding a sodium carbonate solution into the silica gel solution, and keeping stirring in the adding process, wherein the added molar weight of the sodium carbonate is not less than the sum of the added molar weights of the copper nitrate and the strontium nitrate;
and after stirring, standing for 12-14 h, washing with water until the pH of washing liquor is close to 7, vacuum drying, roasting in a muffle furnace, and finally introducing hydrogen for reduction reaction.
2. The process for preparing hydrogen oil by high-temperature garbage conversion according to claim 1, wherein in step S1, the step of heating the mixed mixture to 70-80 ℃, specifically comprises the following steps:
placing the mixed mixture into a sealed container, extracting air in the sealed container until the atmospheric pressure in the sealed container is reduced to 0.04MPa, and gradually increasing the temperature in the sealed container from room temperature to 35 ℃ at the temperature increase rate of 2 ℃/min; keeping the temperature at 35 ℃ for 30min;
then the temperature in the sealed container is gradually increased to 60 ℃ at the temperature increasing rate of 4 ℃/min; keeping the temperature at 60 ℃ for 30min;
gradually increasing the temperature in the sealed container to 100 ℃ at the temperature increase rate of 4 ℃/min; keeping the temperature at 100 ℃ for 30min;
finally, naturally cooling to 70-80 ℃.
3. The process for preparing hydrogen oil by high-temperature conversion of garbage according to claim 1, wherein the w/w concentration of the biomass garbage is 64%, and the w/w concentration of phosphite is 1.2%.
4. The process for preparing hydrogen oil by high-temperature conversion of garbage according to claim 1, wherein the acid solution is a nitric acid solution.
5. The process for preparing hydrogen oil by high-temperature conversion of garbage according to claim 1, wherein the molar amount of sodium carbonate added is slightly larger than the sum of the molar amounts of copper nitrate and strontium nitrate added.
6. The process for preparing hydrogen oil by high-temperature garbage conversion according to claim 1, wherein the hydrogen gas is introduced after the reduction reaction is completed when the reduction reaction is performed by introducing the hydrogen gas, and the introduction of the hydrogen gas can be stopped until the temperature naturally approaches room temperature.
7. The process for preparing hydrogen oil by high-temperature garbage conversion according to claim 1, wherein hydrogen is introduced for reduction reaction at a temperature of 200-280 ℃.
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