CN113913203A - Method for preparing hydrogen from organic garbage - Google Patents
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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Abstract
The invention relates to a method for preparing hydrogen from organic garbage, which comprises the steps of carrying out high-temperature anaerobic pyrolysis and catalytic reforming conversion treatment on the organic garbage, pretreating hydrogen gas containing hydrogen sulfide and hydrogen chloride, improving the extraction rate of the hydrogen, recycling products in each step, realizing near zero emission and no pollution.
Description
Technical Field
The invention belongs to the technical field of garbage treatment, and particularly relates to a method for preparing hydrogen from organic garbage.
Background
The hydrogen energy is a good green energy without carbon dioxide emission, carbon peak reaching, carbon neutralization and metallurgical reduction iron making and rockets can not leave hydrogen, domestic hydrogen stations are more and more built, and particularly, after the problem of solid hydrogen storage technology is solved by the cross of Western-style safety, the hydrogen energy has an explosion period. China writes hydrogen energy into government work reports, develops a cheap and super-green hydrogen production mode, and has very good market prospect.
The hydrogen produced by fossil energy currently accounts for about 90% of the total output: the carbon dioxide and the like which are discharged into the atmosphere are named as grey hydrogen; hydrogen is produced by fossil energy but hydrogen produced by recovering and storing carbon dioxide is blue hydrogen; hydrogen produced by electrolyzing water through solar power generation and wind power generation is green hydrogen, but consumes a large amount of non-ferrous metals such as fresh water, copper plates and the like; the method for preparing hydrogen by pyrolyzing garbage is the best green hydrogen capable of realizing negative carbon emission at present.
The most widespread and popular treatment method for treating household garbage is incineration power generation, which is more environment-friendly than thermal power generation using fossil energy coal and the like, but the incineration power generation has large carbon dioxide emission, fly ash, dioxin emission and the like, and is not suitable for garbage treatment.
The domestic garbage treatment includes incineration, gasification and pyrolysis. The incineration can only generate electricity, most of the remaining processes select gasification, for example, the process for preparing hydrogen by adopting an ultrahigh-temperature plasma reaction torch improved by the Japanese technology in California of America is an improved type of gasification, the reaction is violent, the control is not good, and the quantity of treated garbage is not large. The rest of units have pyrolysis, the mixed gas is prepared and then used for heating or power generation, and few units prepare hydrogen; even if the hydrogen is prepared by adopting a physical separation method, the method for preparing the hydrogen by fossil energy generally adopts a cryogenic separation or Pressure Swing Adsorption (PSA) physical separation method to obtain 99.999 percent of hydrogen. The cryogenic and PSA processes are relatively costly, and the existing waste treatment processes are specifically shown in Table 1.
TABLE 1
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the method for preparing the hydrogen by using the organic garbage, and the method has the advantages of high hydrogen preparation amount, low cost and environmental friendliness.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing hydrogen from organic garbage comprises high-temperature anaerobic pyrolysis treatment and catalytic reforming conversion treatment.
Further, the method also comprises the treatment of hydrogen sulfide and acidic substances.
Further, the method for preparing hydrogen from organic garbage comprises the following steps:
(1) crushing, dehydrating and intelligently sorting organic garbage, and adding a catalyst to obtain RDF fuel or RDF fuel rods;
(2) performing high-temperature anaerobic pyrolysis treatment on the RDF fuel or RDF fuel rods in a rotary kiln, recovering products to obtain mixed gas containing heavy tar and high-temperature pyrolytic carbon, performing heat exchange and cooling 1 treatment on flue tail gas of a heating gas source, and generating steam by utilizing waste heat;
(3) the mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon are continuously heated and decomposed in the catalytic reforming conversion rotary kiln, steam reforming is carried out to prepare carbon monoxide and hydrogen, the carbon monoxide is catalytically converted to prepare hydrogen, the carbon generates water gas, and the product is subjected to heat exchange and cooling 2 treatment to obtain light tar and synthetic gas;
(4) treating hydrogen sulfide and acidic substances by the synthetic gas through a washing tower A, and increasing the yield by a small amount of hydrogen to obtain combustible gas;
(5) and (3) absorbing residual trace carbon monoxide gas by the combustible gas through a washing tower B, then introducing the combustible gas into a sodium hydroxide washing tower to purify hydrogen, and purifying and separating the hydrogen through a water vapor separation tower B to obtain purified hydrogen.
Furthermore, the organic garbage is one or more of domestic garbage, crop straws, sawdust, organic fertilizer, sludge, carbide slag, petroleum garbage, decoration garbage, landfill garbage and marine garbage.
Further, the mass of the catalyst in the step (1) accounts for 8-18% of the mass of the RDF fuel rod, and the catalyst is one or more of carbide slag, sludge, dolomite, iron blocks and nickel-based catalysts.
Further, the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5: 2.
Further, the temperature of the high-temperature anaerobic pyrolysis in the step (2) is 800-.
Further, the mixed gas comprises carbon monoxide, hydrogen and carbon dioxide.
Further, the flue tail gas in the step (2) is subjected to heat exchange and temperature reduction through a waste heat boiler and an economizer to recover heat, and meanwhile, water vapor is generated.
In the high-temperature anaerobic pyrolysis treatment, in order to fix sulfur and chlorine to inhibit dioxin and reduce NOx generation, the hydrogen yield is increased, the temperature is quickly raised during pyrolysis, air is isolated, the temperature is increased to 1000 ℃ at the high temperature of 800-2+CO2Etc.). The pyrolysis flue tail gas is cooled by the waste heat boiler and the economizer to recover heat, and simultaneously, water vapor is generated.
Further, the small molecule gas obtained by pyrolysis of the heavy tar and the steam in the catalytic reforming conversion rotary kiln in the step (3) comprises hydrogen and carbon monoxide;
further, the heavy tar and the steam generate a large amount of water gas in the catalytic reforming conversion rotary kiln through the steam and the pyrolytic carbon;
further, the heavy tar and steam generate a large amount of hydrogen and carbon dioxide in the catalytic reforming shift rotary kiln.
Further, the temperature of the pyrolytic carbon in the catalytic reforming conversion rotary kiln in the step (3) is 800-950 ℃, and the catalyst in the thermal decomposition is one or more of carbide slag, sludge, dolomite, iron blocks and nickel-based catalysts.
Further, the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5: 2.
The catalyst contains various substances containing elements such as calcium, magnesium, aluminum, iron, titanium and the like, and the residue is chelated at high temperature in a lattice combination state, so that the catalyst can be harmless.
The water vapor and the carbon dioxide are used as activators to activate the catalyst, and the water vapor and the carbon dioxide are products in the reaction without adding other activators additionally.
The mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon are in the presence of a catalyst H2O and CO2Obtaining a light tar and a small molecular gas mixture under catalytic reforming conversion of an activating agent, wherein the small molecular gas mixture mainly comprises carbon monoxide and hydrogen; steam reforming to produce carbon monoxide and hydrogen; the carbon monoxide is catalytically transformed to prepare hydrogen; the char produces water gas. And (3) performing heat exchange and cooling again to obtain light tar and synthesis gas, wherein the involved chemical reaction equation is as follows:
steam reforming: cnHm+nH2O＝nCO+(n+m/2)H2
At high temperature: c(s) + H2O(g)＝CO(g)+H2(g)。
Further, the washing column A described in the step (4) includes FeCl-containing liquid3The front tower of the chlorine-sulfur washing tower and the rear tower of the chlorine-sulfur washing tower containing iron blocks.
Further, the material containing FeCl3The front tower of the chlorine-sulfur washing tower is used for treating hydrogen sulfide, and the rear tower of the chlorine-sulfur washing tower containing iron blocks is used for treating acidic substances.
The liquid in the front tower is continuously pumped to the rear tower, the rear tower and the front tower are provided with gravity pipes, and the chemical reaction equations generated in the front tower and the rear tower are respectively as follows:
H2S+2FeCl3＝2FeCl2+2HCl+S↓；
Fe+2HCl＝FeCl2+H2↑。
the reaction of iron and hydrochloric acid increases the production of a small amount of hydrogen.
Further, in the step (5), the washing tower B contains ammoniacal solution of cuprous chloride.
The combustible gas absorbs the trace carbon monoxide gas left in the last step through the washing tower B, and generates a compound cuprous carbonyl chloride, the CO is thoroughly removed, and the hydrogen is purified, wherein the chemical reaction equation is as follows:
2CuCl+2CO+2H2O＝＝＝＝[Cu2Cl2(CO)2·2H2O]；
and (3) adsorbing and purifying hydrogen in a sodium hydroxide washing tower by the produced carbon dioxide:
CO2+2NaOH＝Na2CO3+H2O。
and purifying and separating by a water-vapor separation tower B to obtain a small amount of sodium carbonate solution, and removing acidic substances such as sulfur dioxide and the like by using a flue tail gas washing tower, so that the flue tail gas is discharged up to the standard, and finally, a large amount of purified hydrogen flows into an aluminum alloy tank for temporary storage.
Compared with the prior art, the invention has the beneficial effects that:
according to the method, organic garbage is subjected to high-temperature anaerobic pyrolysis treatment, heavy tar catalytic reforming conversion treatment and hydrogen sulfide and chlorine chloride gas pretreatment, so that the extraction rate of hydrogen is improved, products in all steps are recycled, near zero emission is realized, no pollution is caused, and compared with a cryogenic process and a pressure swing adsorption process, the method provided by the invention has the advantages that the cost is obviously reduced, and the method is green and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a process flow diagram of a method for preparing hydrogen from organic garbage.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Fig. 1 shows a process flow chart of the method for preparing hydrogen from organic garbage.
The method for preparing hydrogen from organic garbage comprises high-temperature anaerobic pyrolysis treatment, catalytic reforming conversion treatment and treatment of hydrogen sulfide and acidic substances, and the specific method is shown in examples 1-3.
Example 1
The method for preparing hydrogen from household garbage comprises the following steps:
(1) crushing, dehydrating and intelligently sorting out organic matters from household garbage, adding a catalyst to obtain the RDF fuel rod, wherein the mass of the catalyst accounts for 8% of the mass of the RDF fuel rod, and the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5: 2;
(2) performing high-temperature anaerobic pyrolysis treatment on the RDF fuel rod in a rotary kiln, wherein the temperature of the high-temperature anaerobic pyrolysis is 800 ℃, continuously feeding, continuously discharging carbon, and continuously recovering the generated mixed gas containing heavy tar, wherein the mixed gas is CO + H2+CO2The tail gas of the flue of the heating gas source is cooled by a waste heat boiler and an economizer to recover heat, and steam is generated in the process of recovering the heat;
(3) the mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon are continuously heated and decomposed in the catalytic reforming conversion rotary kiln, the temperature of the pyrolytic carbon in the catalytic reforming conversion rotary kiln is 800 ℃, the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5:2, and the catalyst and H are mixed2O and CO2Under the reforming of an activating agent, steam reforming is carried out to prepare carbon monoxide and hydrogen, the carbon monoxide is catalyzed and converted to prepare hydrogen, the carbon generates water gas, and the product is subjected to heat exchange and temperature reduction 2 treatment to obtain light tar and synthesis gas;
(4) treating hydrogen sulfide and acidic substances by the synthetic gas through a washing tower A to increase the yield of a small amount of hydrogen, wherein the washing tower A comprises FeCl3The front tower of the chlorine-sulfur washing tower and the rear tower of the chlorine-sulfur washing tower containing iron blocks are mixed with other hydrogen sulfide treated by the front tower, then the hydrogen chloride and other acidic substances are treated by the rear tower, the rear tower and the front tower are provided with self-flowing pipes, and the liquid of the front tower is continuously pumped to the rear towerIn the tower, controlling the pH values of the solution in the front tower and the solution in the rear tower, and purifying and separating the solution in the water-vapor separation tower A to obtain treated mixed gas;
(5) absorbing residual trace carbon monoxide gas by the combustible gas through a washing tower B, enabling the washing tower B to contain an ammonia solution of cuprous chloride to generate a compound cuprous carbonyl chloride, thoroughly removing carbon monoxide, purifying hydrogen, then enabling the hydrogen to enter a sodium hydroxide washing tower for full reaction, controlling the pH value of the solution, finally purifying and separating the solution through a water-vapor separation tower B to obtain a small amount of sodium carbonate solution, and utilizing the small amount of sodium carbonate solution to a flue tail gas washing tower to remove acidic substances such as sulfur dioxide and the like, enabling the flue tail gas to reach the standard and be discharged, and finally enabling the obtained purified hydrogen to flow into an aluminum alloy tank for temporary storage.
Example 2
The method for preparing hydrogen by using crop straws comprises the following steps:
(1) crushing crop straws, dehydrating, intelligently sorting out organic matters, adding a catalyst to obtain the RDF fuel, wherein the mass of the catalyst accounts for 13% of the mass of the RDF fuel, and the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5: 2;
(2) performing high-temperature anaerobic pyrolysis treatment on the RDF fuel in a rotary kiln, wherein the temperature of the high-temperature anaerobic pyrolysis is 900 ℃, continuously feeding, continuously discharging carbon, and continuously recovering the generated mixed gas containing heavy tar, wherein the mixed gas is CO + H2+CO2The tail gas of the flue of the heating gas source is cooled by a waste heat boiler and an economizer to recover heat, and steam is generated in the process of recovering the heat;
(3) the mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon are continuously heated and decomposed in the catalytic reforming conversion rotary kiln, the temperature of the pyrolytic carbon in the catalytic reforming conversion rotary kiln is 875 ℃, the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5:2, and the catalyst and H are mixed2O and CO2Under the reforming of an activating agent, steam reforming is carried out to prepare carbon monoxide and hydrogen, the carbon monoxide is catalyzed and converted to prepare hydrogen, the carbon generates water gas, and the product is subjected to heat exchange and temperature reduction 2 treatment to obtain light tar and synthesis gas;
(4) treating hydrogen sulfide and acidic substances by the synthetic gas through a washing tower A to increase the yield of a small amount of hydrogen, wherein the washing tower A comprises FeCl3The front tower of the chlorine-sulfur washing tower and the rear tower of the chlorine-sulfur washing tower containing iron blocks are mixed with other hydrogen sulfide treated by the front tower, then acidic substances such as hydrogen chloride and the like are treated by the rear tower, the rear tower and the front tower are provided with self-flowing pipes, liquid in the front tower is continuously pumped into the rear tower, the pH value of the solution in the front tower and the rear tower is controlled, and the treated mixed gas is purified and separated by the water-vapor separation tower A;
(5) absorbing residual trace carbon monoxide gas by the combustible gas through a washing tower B, enabling the washing tower B to contain an ammonia solution of cuprous chloride to generate a compound cuprous carbonyl chloride, thoroughly removing carbon monoxide, purifying hydrogen, then enabling the hydrogen to enter a sodium hydroxide washing tower for full reaction, controlling the pH value of the solution, finally purifying and separating the solution through a water-vapor separation tower B to obtain a small amount of sodium carbonate solution, and utilizing the small amount of sodium carbonate solution to a flue tail gas washing tower to remove acidic substances such as sulfur dioxide and the like, enabling the flue tail gas to reach the standard and be discharged, and finally enabling the obtained purified hydrogen to flow into an aluminum alloy tank for temporary storage.
Example 3
The method for preparing hydrogen from petroleum waste comprises the following steps:
(1) crushing, dehydrating and intelligently sorting out organic matters from petroleum waste, and adding a catalyst to obtain the RDF fuel rod, wherein the mass of the catalyst accounts for 18% of the mass of the RDF fuel rod, and the catalyst is prepared from carbide slag, dolomite and iron blocks according to the mass ratio of 3:5: 2;
(2) performing high-temperature anaerobic pyrolysis treatment on the RDF fuel rod in a rotary kiln, wherein the temperature of the high-temperature anaerobic pyrolysis is 1000 ℃, and the generated mixed gas containing heavy tar is continuously fed, continuously discharged and continuously recycled, wherein the mixed gas is CO + H2+CO2The tail gas of the flue of the heating gas source is cooled by a waste heat boiler and an economizer to recover heat, and steam is generated in the process of recovering the heat;
(3) the mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon continue to be used in the catalytic reforming conversion rotary kilnHeating for decomposition, catalytic reforming for converting pyrolytic carbon in rotary kiln at 950 deg.C, and preparing catalyst from carbide slag, dolomite and iron block at mass ratio of 3:5:22O and CO2Under the reforming of an activating agent, steam reforming is carried out to prepare carbon monoxide and hydrogen, the carbon monoxide is catalyzed and converted to prepare hydrogen, the carbon generates water gas, and the product is subjected to heat exchange and temperature reduction 2 treatment to obtain light tar and synthesis gas;
(4) treating hydrogen sulfide and acidic substances by the synthetic gas through a washing tower A to increase the yield of a small amount of hydrogen, wherein the washing tower A comprises FeCl3The front tower of the chlorine-sulfur washing tower and the rear tower of the chlorine-sulfur washing tower containing iron blocks are mixed with other hydrogen sulfide treated by the front tower, then acidic substances such as hydrogen chloride and the like are treated by the rear tower, the rear tower and the front tower are provided with self-flowing pipes, liquid in the front tower is continuously pumped into the rear tower, the pH value of the solution in the front tower and the rear tower is controlled, and the treated mixed gas is purified and separated by the water-vapor separation tower A;
(5) absorbing residual trace carbon monoxide gas by the combustible gas through a washing tower B, enabling the washing tower B to contain an ammonia solution of cuprous chloride to generate a compound cuprous carbonyl chloride, thoroughly removing carbon monoxide, purifying hydrogen, then enabling the hydrogen to enter a sodium hydroxide washing tower for full reaction, controlling the pH value of the solution, finally purifying and separating the solution through a water-vapor separation tower B to obtain a small amount of sodium carbonate solution, and utilizing the small amount of sodium carbonate solution to a flue tail gas washing tower to remove acidic substances such as sulfur dioxide and the like, enabling the flue tail gas to reach the standard and be discharged, and finally enabling the obtained purified hydrogen to flow into an aluminum alloy tank for temporary storage.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The method for preparing hydrogen from organic garbage is characterized by comprising high-temperature anaerobic pyrolysis treatment and catalytic reforming conversion treatment, and preferably further comprising treatment of hydrogen sulfide and acidic substances.
2. The method for preparing hydrogen from organic garbage according to claim 1, comprising the following steps:
(1) crushing, dehydrating and intelligently sorting organic garbage, and adding a catalyst to obtain RDF fuel or RDF fuel rods;
(2) performing high-temperature anaerobic pyrolysis treatment on the RDF fuel or RDF fuel rods in a rotary kiln, recovering products to obtain mixed gas containing heavy tar and high-temperature pyrolytic carbon, performing heat exchange and cooling 1 treatment on flue tail gas of a heating gas source, and generating steam by utilizing waste heat;
(3) the mixed gas containing the heavy tar, the steam and the high-temperature pyrolytic carbon are continuously heated and decomposed in the catalytic reforming conversion rotary kiln, steam reforming is carried out to prepare carbon monoxide and hydrogen, the carbon monoxide is catalytically converted to prepare hydrogen, the carbon generates water gas, and the product is subjected to heat exchange and cooling 2 treatment to obtain light tar and synthetic gas;
(4) treating hydrogen sulfide and acidic substances by the synthetic gas through a washing tower A, and increasing the yield by a small amount of hydrogen to obtain combustible gas;
(5) and (3) absorbing residual trace carbon monoxide gas by the combustible gas through a washing tower B, then introducing the combustible gas into a sodium hydroxide washing tower to purify hydrogen, and purifying and separating the hydrogen through a water vapor separation tower B to obtain purified hydrogen.
3. The method for preparing hydrogen from organic garbage according to claim 1, wherein the organic garbage is one or more of domestic garbage, crop straw, sawdust, organic fertilizer, sludge, carbide slag, petroleum garbage, decoration garbage, landfill garbage and marine garbage.
4. The method for preparing hydrogen from organic garbage according to claim 1, wherein the mass of the catalyst in the step (1) accounts for 8-18% of the mass of the RDF fuel rod, and the catalyst is one or more of carbide slag, sludge, dolomite, iron blocks and nickel-based catalysts.
5. The method for preparing hydrogen from organic garbage as claimed in claim 1, wherein the temperature of the high temperature anaerobic pyrolysis in the step (2) is 800-1000 ℃, preferably, the mixed gas comprises carbon monoxide, hydrogen and carbon dioxide.
6. The method for preparing hydrogen from organic garbage according to claim 1, wherein the flue tail gas in the step (2) is subjected to heat exchange and temperature reduction by a waste heat boiler and an economizer to recover heat, and steam is generated at the same time.
7. The method for preparing hydrogen from organic garbage according to claim 1, wherein the small molecule gas obtained by pyrolysis of heavy tar and steam in the catalytic reforming conversion rotary kiln in the step (3) comprises hydrogen and carbon monoxide;
preferably, the heavy tar and the steam generate a large amount of water gas in the catalytic reforming shift rotary kiln through the steam and the pyrolytic carbon;
preferably, the heavy tars and steam form significant amounts of hydrogen and carbon dioxide in the catalytic reforming shift rotary kiln with steam and carbon monoxide.
8. The method for preparing hydrogen from organic garbage as claimed in claim 1, wherein the temperature of the pyrolytic carbon in the catalytic reforming conversion rotary kiln in the step (3) is 800-.
9. The method for preparing hydrogen from organic garbage according to claim 1, wherein the washing tower A in step (4) comprises FeCl3The front tower of the chlorine-sulfur washing tower and the rear tower of the chlorine-sulfur washing tower containing iron blocks, preferably, the tower containsFeCl3The front tower of the chlorine-sulfur washing tower is used for treating hydrogen sulfide, and the rear tower of the chlorine-sulfur washing tower containing iron blocks is used for treating acidic substances.
10. The method for preparing hydrogen from organic garbage according to claim 1, wherein the washing tower B in the step (5) contains ammoniacal solution of cuprous chloride.
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| CN117945344A (en) * | 2024-03-27 | 2024-04-30 | 中鹏未来有限公司 | Method for preparing hydrogen by pulping by mixing pyrolysis oil and carbon of household garbage |
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