CN114733527A - Preparation method of Ca-Ni ash-based catalyst and hydrogen-rich synthesis gas - Google Patents
Preparation method of Ca-Ni ash-based catalyst and hydrogen-rich synthesis gas Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention belongs to the technical field of solid waste recycling, and particularly relates to a preparation method of a Ca-Ni ash-based catalyst and hydrogen-rich synthesis gas. The invention provides a preparation method of a Ca-Ni ash-based catalytic material, which comprises the following steps of carrying out hydrothermal treatment on sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner, mixing, dehydrating, adding nickel salt, mixing, grinding, crushing and carrying out pyrolysis treatment, wherein a solid phase obtained by pyrolysis is the Ca-Ni ash-based catalytic material. The invention adds the conditioner into the sludge in the hydrothermal treatment process, then adds the nickel salt for pyrolysis treatment, can obtain the Ca-Ni ash-based catalytic material, and the material fully well performs solid-phase waste residue after the hydrothermal pyrolysis treatment on the sludgeAnd the catalyst can be used as CO2The capture agent promotes the forward direction of the water gas reaction.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling, and particularly relates to a preparation method of a Ca-Ni ash-based catalyst and hydrogen-rich synthesis gas.
Background
Sludge is a solid precipitate generated in the process of treating water and sewage, and the sludge contains a large amount of organic matters, pathogenic bacteria, heavy metals, inorganic matters and the like, so that the sludge is effectively and safely treated, and the effective recycling and energy conversion of the organic matters in the sludge are realized to become the main development direction of the sludge treatment process. The gasification technology is one of the treatment technologies for realizing sludge stabilization and recycling, and has great development potential due to the characteristics of energy recovery, sludge reduction and harmlessness, short treatment period and the like. However, the by-products such as tar and the like are inevitably generated in the conventional gasification process, so that the gasification conversion efficiency is reduced, and meanwhile, the stable operation of gasification equipment is seriously influenced due to the characteristics of high viscosity and high water content of the tar. On the other hand, in the conventional sludge gasification system, the energy consumption of the sludge heat drying unit accounts for about 80% of the whole system. Therefore, how to realize deep dehydration of sludge by a high-efficiency and low-consumption mode to replace a sludge drying unit and simultaneously improve the gasification efficiency of the sludge and reduce the yield of tar becomes the main technical bottleneck of popularization and application of the technology.
As an important sludge dewatering conditioning technology, the hydrothermal technology does not generate phase state conversion of water in the treatment process, so that the energy consumption of the hydrothermal technology is obviously lower than that of a heat drying technology. The prior art discloses a sludge high-efficiency energy treatment method based on hydrothermal pretreatment, which comprises the following steps of adding an iron-based conditioner into sludge for hydrothermal treatment, carrying out pyrolysis treatment on obtained gas in the second step, and carrying out anaerobic digestion treatment on the gas after the pyrolysis treatment to obtain methane in the third step.
However, in the sludge treatment method disclosed in the prior art, the solid phase after pyrolysis treatment is not effectively treated.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the solid phase is not effectively treated after the pyrolysis treatment in the prior art, thereby providing a preparation method of the Ca-Ni ash-based catalyst and the hydrogen-rich synthesis gas.
Therefore, the invention provides the following technical scheme,
the invention provides a preparation method of Ca-Ni ash-based catalytic material, which comprises the following steps,
performing hydrothermal treatment on the sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner, mixing, dehydrating, adding nickel salt, mixing, grinding, crushing and performing pyrolysis treatment, wherein the solid phase obtained by pyrolysis is a Ca-Ni ash-based catalytic material.
Optionally, the conditioning agent is tannic acid and a calcium-based conditioning agent.
Optionally, the calcium-based conditioning agent comprises one or more of calcium oxide, calcium hydroxide, calcium carbonate;
and/or the mass ratio of the tannin to the calcium-based conditioner is (1-2): (1-2).
Optionally, the sludge comprises one or more of primary sludge, excess sludge, concentrated sludge, dewatered sludge and digested sludge;
and/or the solid content of the sludge is 1-25%.
Optionally, when the temperature of the hydrothermal treatment is 60-120 ℃, the pressure of the hydrothermal treatment is 0.02-0.2 MPa;
and/or the addition amount of the conditioner is 0.1-0.4g/g based on the dry weight of the sludge.
Optionally, when the temperature of the hydrothermal treatment is 120-160 ℃, the pressure of the hydrothermal treatment is 0.2-0.65 MPa;
and/or the addition amount of the conditioner is 0.05-0.3g/g based on the dry weight of the sludge.
Optionally, the nickel salt includes one or more of nickel nitrate and nickel chloride;
and/or the addition amount of the nickel salt is 3-7% of the dry weight of the sludge based on the dry weight of the sludge.
Optionally, the pyrolysis temperature is 400-600 ℃;
the pyrolysis time is 30-90 min.
The invention also provides a preparation method of the hydrogen-rich synthesis gas, which comprises the following steps,
and (2) carrying out hydrothermal treatment on the sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner for mixing, dehydrating, then adding nickel salt for mixing, grinding and crushing, then carrying out pyrolysis treatment, adding tar and gas-phase products obtained by pyrolysis into the Ca-Ni catalyst prepared by the preparation method for carrying out steam gasification treatment, and obtaining hydrogen-rich synthesis gas after gasification.
Alternatively, the above-described method for producing a hydrogen-rich synthesis gas satisfies at least one of the following (1) to (4):
(1) the mass ratio of the Ca-Ni catalyst to the water vapor is (1-2): (1-3);
(2) the addition amount of the Ca-Ni catalyst is 40-100% of the dry weight of the sludge by taking the dry weight of the sludge as a reference;
(3) the gasification temperature is 700-1000 ℃;
(4) the gasification time is 15-60 min.
Specifically, the invention provides the following technical scheme,
step one, performing hydrothermal pretreatment on sludge generated by a sewage plant with a solid content of 1-25 percent:
the working condition I is as follows: when the hydrothermal pretreatment conditions are as follows: hydrothermal temperature is 60-120 ℃, and treatment time is 5-60 min:
placing sludge generated by a sewage treatment plant with a solid content of 1-25% in a hydrothermal high-pressure reaction kettle, adding a conditioner, fully mixing, wherein the addition amount of the conditioner is 0.1-0.4g/g (dry weight (TS)), keeping for 5-60min under the conditions of 60-120 ℃ and 0.02-0.2MPa, adding a calcium-based conditioner into the conditioned sludge, uniformly stirring, and then mechanically dehydrating to ensure that the solid content of the dehydrated sludge is lower than 50%.
Working conditions are as follows: when the hydrothermal pretreatment conditions are as follows: the hydrothermal temperature is 120-:
placing sludge generated by a sewage treatment plant with a solid content of 1-25% in a hydrothermal high-pressure reaction kettle, and keeping for 5-60min under the conditions of high temperature and high pressure; the reaction conditions of the hydrothermal pretreatment are 120-160 ℃ and 0.2-0.65 MPa. After hydrothermal treatment, adding a conditioner into the cooled sludge for conditioning, wherein the addition amount of the conditioner is 0.05-0.3g/g (TS), stirring for 1-3min, standing for 10-20min, adding a calcium-based conditioner into the conditioned sludge, uniformly stirring, and then mechanically dehydrating to ensure that the solid content of the dehydrated sludge is lower than 50%.
And step two, adding one or more of nickel nitrate or nickel chloride solids into the conditioned and reformed dehydrated sludge, and grinding and crushing the mixture to obtain the sludge with the particle size of 0.05-2 mm.
And step three, performing pyrolysis treatment on the crushed sludge sample, wherein the pyrolysis temperature in the pyrolysis stage is 400-600 ℃, preparing a solid phase product which is a Ni/Ca catalytic material, and allowing other products to enter a gasification unit for next treatment.
And step four, carrying out steam gasification conversion on tar and gas-phase products generated by the pyrolysis unit, adding a catalyst into the gasification furnace, and carrying out catalytic reforming on tar, wherein the gasification temperature of the reaction stage is 700-.
The technical proposal provided by the invention has the advantages that,
1. the invention provides a preparation method of a Ca-Ni ash-based catalytic material, which comprises the following steps of carrying out hydrothermal treatment on sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner, mixing, dehydrating, adding nickel salt, mixing, grinding, crushing and carrying out pyrolysis treatment, wherein a solid phase obtained by pyrolysis is the Ca-Ni ash-based catalytic material. The invention adds the conditioner into the sludge in the hydrothermal treatment process, then adds the nickel salt for pyrolysis treatment, can obtain the Ca-Ni ash-based catalytic material, the material fully utilizes the solid-phase waste residue after the hydrothermal pyrolysis treatment of the sludge, and the catalyst can be used as CO2The capture agent promotes the forward direction of the water gas reaction.
2. The invention adopts tannic acid as a conditioner in the hydrothermal treatment process. Due to the unique structural characteristics of the tannic acid, the tannic acid is combined with hydrophilic protein in the sludge and is fixed in a solid-phase product, so that the dehydration performance of the sludge after hydrothermal treatment is greatly improved, the concentration of nitrogen-containing pollutants in the filtrate is obviously reduced, and the treatment difficulty and cost of the filtrate after dehydration are reduced. For the dewatered sludge generated after hydrothermal treatment, the addition of the tannic acid obviously improves the stability of nitrogen-containing organic matters in a solid-phase product and reduces the yield of nitrogen-containing pollutants in the gasification process.
3. The invention adopts a hydrothermal treatment process, after the sludge is subjected to hydrothermal treatment, the structure of sludge flocs is destroyed, combined water is converted into free water, and organic matters in the sludge are dissolved out and hydrolyzed to realize quality-divided reforming. As a pretreatment process of sludge gasification, the method fundamentally changes the reaction path in the gasification process of organic matters in the sludge and realizes the preparation of hydrogen-rich gas. Meanwhile, the hydrothermal condition adopted by the invention is mild, the refractory organic matters generated by polycondensation reaction such as Maillard reaction and the like are avoided, and the treatment difficulty and cost of the filtrate after sludge dehydration are reduced.
4. According to the invention, according to different polymerization degrees and space structures of organic matters under different hydrothermal conditions, different adding modes are adopted, so that effective fixation and stabilization conditioning of hydrophilic protein substances in sludge are realized.
5. The invention also provides a preparation method of the hydrogen-rich synthetic gas, which comprises the following steps of carrying out hydrothermal treatment on the sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner for mixing, dehydrating, adding nickel salt for mixing, grinding and crushing, carrying out pyrolysis treatment, adding tar and gas-phase products obtained by pyrolysis into the Ca-Ni ash-based catalyst prepared by the preparation method for carrying out steam gasification treatment, and obtaining the hydrogen-rich synthetic gas after gasification. The Ca-Ni ash-based catalyst is adopted for steam gasification treatment, contains a large amount of Ni and CaO with higher dispersity and stronger catalytic activity, and carries out catalytic reforming on tar, thereby promoting the breakage of C-O and C-N bonds in the tar, improving the gasification conversion efficiency of the tar and realizing the directional conversion of the hydrogen-rich gas prepared by gasification.
6. The gasification reaction condition of the sludge is selected from 700 ℃ and 1000 ℃, so that the excessive gasification temperature is avoided, the active metal in the sludge is diffused and sintered in the particles, and the catalytic activity of the gasified catalyst is reduced. The simultaneous production of the hydrogen-rich clean gas fuel and the catalyst is achieved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
This example provides a method for preparing a Ca-Ni ash-based catalyst,
placing 80kg of dewatered sludge with a solid content of 10% into an inner container of a hydrothermal reaction kettle with an effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, after the sludge is cooled, adding 0.05g/g (TS) of tannic acid conditioner into the sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of CaO conditioner into the sludge, wherein the mass ratio of the tannic acid to the CaO conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the sludge after dehydration is reduced to 20%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 2
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 400kg of concentrated sludge with the solid content of 5% into a liner of a hydrothermal reaction kettle, simultaneously adding 0.3g/g (TS) of a tannic acid conditioner, uniformly stirring, setting the temperature at 120 ℃ and the pressure at 0.2MPa, maintaining for 30min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, cooling the sludge, adding 0.15g/g (TS) of CaCO3 conditioner, stirring and mixing the tannic acid and the CaO conditioner in a mass ratio of 2:1, performing frame filter pressing dehydration, and reducing the solid content of the dewatered sludge to 40%. The produced wet mud cake is ground with 4 percent (TS) of nickel nitrate and crushed into particles with the particle size of 0.21-1.54mm, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 500 ℃, and the pyrolysis time is 60 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a method for producing a hydrogen-rich synthesis gas,
the tar and other products generated by pyrolysis enter a gasification system for gasification, the pyrolysis temperature is 700 ℃, the addition amount of the Ca-Ni ash-based catalyst is 70% (TS), the water-carbon ratio is 1.7:1, and the gasification time is 30 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 3
This example provides a method for preparing a Ca-Ni ash-based catalyst,
placing 320kg of municipal sludge with the solid content of 8% into a liner of a hydrothermal reaction kettle, setting the temperature at 140 ℃ and the pressure at 0.36MPa, maintaining for 45min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, cooling the sludge, adding 0.2g/g (TS) of tannic acid conditioner, fully stirring for 2min, and standing for 15 min. Adding Ca (OH) into the sludge20.15g/g (TS) of conditioner, wherein the mass ratio of the tannic acid to the CaO conditioner is 4:3, stirring and mixing are carried out, frame filter pressing dehydration is carried out, and the solid content of the dehydrated sludge is reduced to 35%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.12-1.21mm by 5.5 percent (TS) of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 90 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a method for producing a hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the pyrolysis temperature is 900 ℃, the addition amount of the Ca-Ni ash-based catalyst is 90 percent (TS), the water-carbon ratio is 1.9:1, and the gasification time is 45 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 4 (end point data compared to example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
300kg of concentrated sludge with the solid content of 1 percent is put into an inner container of a hydrothermal reaction kettle with the effective volume of 100L, the set temperature is 160 ℃, the pressure is 0.65MPa, the temperature is maintained for 5min after the set temperature is reached, water vapor is recovered and is used for preheating sludge in a sludge storage tank, 0.05g/g (TS) of tannic acid conditioner is added into the sludge after the sludge is cooled, the mixture is fully stirred for 2min, and the mixture is kept stand for 15 min. And then adding 0.1g/g (TS) of CaO conditioner into the sludge, wherein the mass ratio of the tannic acid to the CaO conditioner is 1:2, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the sludge after dehydration is reduced to 20%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 90 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 1000 ℃, the addition amount of the Ca-Ni ash-based catalyst is 100 percent (TS), the water-carbon ratio is 2:1, and the gasification time is 60 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 5 (use of the other endpoint value of the data compared to example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 70kg of dewatered sludge with a solid content of 25% into an inner container of a hydrothermal reaction kettle with an effective volume of 100L, setting the temperature at 60 ℃ and the pressure at 0.02MPa, maintaining for 15min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, after the sludge is cooled, adding 0.4g/g (TS) of tannic acid conditioner into the sludge, fully stirring for 2min, and standing for 15 min. And then adding 0.4g/g (TS) of CaO conditioner into the sludge, wherein the mass ratio of the tannic acid to the CaO conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the sludge after dehydration is reduced to 50%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 7 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 400 ℃, and the pyrolysis time is 90 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 700 ℃, the addition amount of the Ca-Ni ash-based catalyst is 100 percent (TS), the water-carbon ratio is 3:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 6 (different substances compared to example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 80kg of digested sludge with a solid content of 10% into an inner container of a hydrothermal reaction kettle with an effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, after the sludge is cooled, adding 0.05g/g (TS) of tannic acid conditioner into the sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of calcium carbonate conditioner into the sludge, wherein the mass ratio of the tannic acid to the calcium carbonate conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the dewatered sludge is reduced to 20%. The produced wet mud cake and 3% of nickel chloride are ground and crushed into particles with the particle size of 0.15-1.05mm, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Example 7 (different materials compared to example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 80kg of excess sludge with the solid content of 10% into an inner container of a hydrothermal reaction kettle with the effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the temperature reaches the set temperature, recovering water vapor and preheating sludge in a sludge storage tank, after cooling the sludge, adding 0.05g/g (TS) of tannic acid conditioner into the sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of calcium hydroxide conditioner into the sludge, wherein the mass ratio of the tannic acid to the calcium hydroxide conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the dewatered sludge is reduced to 20%. The produced wet mud cake is ground with 3% of nickel chloride and crushed into particles with the particle size of 0.15-1.05mm, and then the wet mud cake enters a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a method for producing a hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Comparative example 1 (addition of additional conditioner compared to example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 80kg of dewatered sludge with the solid content of 10% into an inner container of a hydrothermal reaction kettle with the effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the set temperature is reached, recycling water vapor and preheating sludge in a sludge storage tank, adding 0.05g/g (TS) of PAM conditioner into the cooled sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of calcium carbonate conditioner into the sludge, wherein the mass ratio of the tannic acid to the calcium carbonate conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the dewatered sludge is reduced to 30%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Comparative example 2 (comparison with example 1, without tannic acid)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
putting 80kg of dewatered sludge with the solid content of 10% into a liner of a hydrothermal reaction kettle with the effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the set temperature is reached, recycling water vapor and preheating sludge in a sludge storage tank, adding 0.05g/g (TS) of CaO conditioner into the sludge after the sludge is cooled, wherein the mass ratio of tannic acid to the CaO conditioner is 1:1, stirring and mixing, performing frame filter pressing and dewatering, and reducing the solid content of the dewatered sludge to 60%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Comparative example 3 (hydrothermal temperature out of range, comparison with example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
placing 80kg of dewatered sludge with a solid content of 10% into an inner container of a hydrothermal reaction kettle with an effective volume of 100L, setting the temperature at 40 ℃ and the pressure at 0.01MPa, maintaining for 30min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, adding 0.05g/g (TS) of tannic acid conditioner into the cooled sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of CaO conditioner into the sludge, wherein the mass ratio of the tannic acid to the CaO conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the sludge after dehydration is reduced to 60%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
the tar and other products generated by the pyrolysis enter a gasification system for gasification, the gasification temperature is 800 ℃, the addition amount of the Ca-Ni ash-based catalyst is 50 percent (TS), the water-carbon ratio is 2.2:1, and the gasification time is 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Comparative example 4 (preparation of hydrogen-rich syngas without addition of Ca-Ni Gray-based catalyst, compare with example 1)
This example provides a method for preparing a Ca-Ni ash-based catalyst,
placing 80kg of dewatered sludge with a solid content of 10% into an inner container of a hydrothermal reaction kettle with an effective volume of 100L, setting the temperature at 160 ℃ and the pressure at 0.65MPa, maintaining for 30min after the set temperature is reached, recovering water vapor and preheating sludge in a sludge storage tank, after the sludge is cooled, adding 0.05g/g (TS) of tannic acid conditioner into the sludge, fully stirring for 1min, and standing for 20 min. And then adding 0.05g/g (TS) of CaO conditioner into the sludge, wherein the mass ratio of the tannic acid to the CaO conditioner is 1:1, stirring and mixing, and performing frame filter pressing dehydration, wherein the solid content of the sludge after dehydration is reduced to 20%. The produced wet mud cake is ground and crushed into particles with the particle size of 0.15-1.05mm by 3 percent of nickel nitrate, and then the particles enter a pyrolysis system for conversion, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min. The solid phase generated by pyrolysis is the Ca-Ni ash-based catalyst.
The present example also provides a process for the production of hydrogen-rich synthesis gas,
and (3) gasifying tar and other products generated by pyrolysis in a gasification system at the gasification temperature of 800 ℃ for 15 min. Namely, hydrogen-rich synthesis gas and pyrolysis oil are obtained.
Test example
The hydrogen-rich syngas and pyrolysis oil produced in examples 1-7 and comparative examples 1-4 were tested.
The method for testing the yield of the hydrogen-rich synthesis gas comprises the following steps: testing by gas chromatography;
the volume ratio test method of hydrogen in the hydrogen-rich synthesis gas comprises the following steps: testing by gas chromatography;
the yield test method of the pyrolysis oil comprises the following steps: collected with carbon dichloride and tested by solvent evaporation weighing.
The test results were as follows:
according to the table, the coupling of the hydrothermal treatment and the tannic acid effectively improves the dehydration performance of the sludge and realizes the deep dehydration of the sludge. Meanwhile, the tannic acid has a strong chelating effect, and the catalytic performance of the Ca-Ni ash-based catalyst is improved by improving the dispersion degree of the nickel salt solid-phase product, so that the conversion efficiency of the tar catalytic reforming stage is promoted. Different calcium-based conditioning can be used as CO2The capture agent promotes the forward proceeding of the water gas reaction, and further realizes the oriented hydrogen production conversion process of sludge pyrolysis. The necessity, rationality and advancement of the conditioning agents and process parameters employed in this patent are fully demonstrated by the examples.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method for preparing Ca-Ni ash-based catalytic material is characterized by comprising the following steps,
performing hydrothermal treatment on the sludge for 5-60min at the temperature of 60-160 ℃, then adding a conditioner, mixing, dehydrating, adding nickel salt, mixing, grinding, crushing and performing pyrolysis treatment, wherein the solid phase obtained by pyrolysis is a Ca-Ni ash-based catalytic material.
2. The method of claim 1, wherein the conditioning agent is tannic acid and a calcium based conditioning agent.
3. The method for preparing the Ca-Ni ash-based catalytic material of claim 2, wherein the calcium-based conditioning agent comprises one or more of calcium oxide, calcium hydroxide, calcium carbonate;
and/or the mass ratio of the tannic acid to the calcium-based conditioner is (1-2): (1-2).
4. The method for preparing Ca-Ni ash-based catalytic material according to any one of claims 1 to 3, wherein the sludge comprises one or more of primary sludge, excess sludge, thickened sludge, dewatered sludge, digested sludge;
and/or the solid content of the sludge is 1-25%.
5. The method for preparing Ca-Ni ash-based catalytic material according to any one of claims 1 to 4, wherein when the temperature of the hydrothermal treatment is 60 to 120 ℃, the pressure of the hydrothermal treatment is 0.02 to 0.2 MPa;
and/or the addition amount of the conditioner is 0.1-0.4g/g based on the dry weight of the sludge.
6. The method for preparing Ca-Ni ash-based catalytic material as claimed in any one of claims 1 to 4, wherein the pressure of the hydrothermal treatment is 0.2 to 0.65MPa when the temperature of the hydrothermal treatment is 120 ℃ and 160 ℃;
and/or the addition amount of the conditioner is 0.05-0.3g/g based on the dry weight of the sludge.
7. The method for preparing a Ca-Ni ash-based catalytic material according to any one of claims 1 to 6, wherein the nickel salt comprises one or more of nickel nitrate, nickel chloride;
and/or the addition amount of the nickel salt is 3-7% of the dry weight of the sludge based on the dry weight of the sludge.
8. The method for preparing Ca-Ni ash-based catalytic material as claimed in any one of claims 1 to 7, wherein the pyrolysis temperature is 400-600 ℃;
the pyrolysis time is 30-90 min.
9. A method for preparing hydrogen-rich synthesis gas is characterized by comprising the following steps,
performing hydrothermal treatment on sludge at 60-160 ℃ for 5-60min, adding a conditioner, mixing, dehydrating, adding nickel salt, mixing, grinding, crushing, performing pyrolysis treatment, adding tar and gas-phase products obtained by pyrolysis into the Ca-Ni catalyst prepared by the preparation method of any one of claims 1-8, performing steam gasification treatment, and gasifying to obtain hydrogen-rich synthetic gas.
10. The method for producing a hydrogen-rich synthesis gas according to claim 9, characterized by satisfying at least one of the following (1) to (4):
(1) the mass ratio of the Ca-Ni catalyst to the water vapor is (1-2): (1-3);
(2) the addition amount of the Ca-Ni catalyst is 40-100% of the dry weight of the sludge by taking the dry weight of the sludge as a reference;
(3) the gasification temperature is 700-1000 ℃;
(4) the gasification time is 15-60 min.
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