Waste gasification hydrogen production and SOFC coupled heat and power cogeneration system and method

Abstract

The invention discloses a waste gasification hydrogen production and SOFC coupled heat and power cogeneration system and method, and the system comprises a waste drying unit which is used for drying waste; the garbage gasification unit is used for carrying out gasification treatment on the dried garbage; the hydrogen purification unit is used for carrying out purification treatment on crude synthesis gas obtained after garbage gasification; and the SOFC unit is used for generating power through air and the purified fuel, and generated heat supplies heat to the garbage drying unit through the heat exchange unit. Garbage is used as a raw material, combined heat and power of garbage gasification hydrogen production coupled SOFC is achieved through the garbage drying unit, the garbage gasification unit, the garbage purification unit, the SOFC unit and the heat exchange unit, good economic benefits and sustainable operation are achieved, the anode of the SOFC unit is designed, and the stability and the fuel utilization rate of the SOFC unit are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of SOFC, and in particular to a heat and power cogeneration system and method for waste gasification hydrogen production coupled with SOFC. Background Art

[0002] Solid oxide fuel cell (SOFC) is a new type of power generation device with high efficiency, pollution-free, all-solid-state structure, mainly composed of electrolyte, anode, cathode and connector, in which the anode is used to enrich fuel gas and the cathode is used to enrich oxygen.

[0003] At present, the main method of domestic waste incineration is power generation. Although this method has achieved the resource utilization of domestic waste, it has the problems of poor economic benefits and sustainable operation. Waste gasification is a process in which waste releases a large amount of combustible gases such as CO, H2 and CH4 under the action of gasifying agents and high temperatures. The combustible gases formed can be used for SOFC power generation after treatment. However, for existing SOFC fuel electrodes, there are problems with low stability and fuel utilization. Summary of the invention

[0004] Based on the technical problems existing in the background technology, the present invention proposes a heat and power cogeneration system and method of waste gasification hydrogen production coupled with SOFC, which improves the stability of SOFC electrodes and higher fuel utilization.

[0005] The waste gasification hydrogen production coupled with SOFC cogeneration system proposed in the present invention comprises:

[0006] A garbage drying unit, used for drying garbage;

[0007] Garbage gasification unit, used for gasification of dried garbage;

[0008] A hydrogen purification unit is used to purify the raw synthesis gas after garbage gasification;

[0009] The SOFC unit generates electricity through air and purified fuel, and the heat generated is used to heat the garbage drying unit through the heat exchange unit.

[0010] Preferably, the steps of the method for preparing the anode of the SOFC unit are as follows:

[0011] S1: Sr(NO3)3, butyl titanate, siderite, pore former and complexing agent are dispersed in ethylene glycol to form an anode slurry;

[0012] S2: spraying the anode slurry onto the substrate surface and calcining to obtain the anode skeleton;

[0013] S3: dissolving cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in deionized water to obtain an impregnation solution;

[0014] S4: Immerse the anode skeleton in the impregnation solution, and obtain the anode after calcination.

[0015] Preferably, the mass ratio of Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent is 1:0.5-1:0.3-0.5:0.1-0.2:0.01-0.05:0.01-0.03.

[0016] Preferably, the pore-forming agent in S1 is composed of carbon black and polyvinyl alcohol in a mass ratio of 1:0.4-0.8.

[0017] Preferably, the complexing agent in S1 is composed of citric acid and triethanolamine in a mass ratio of 3:1-9.

[0018] Preferably, the structure directing agent in S1 is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride in a mass ratio of 2:1-4.

[0019] Preferably, the calcination temperature in S2 is 900-1200° C. and the calcination time is 3-5 h.

[0020] Preferably, the mass ratio of cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in S3 is 1:1-1.5:0.5-0.8:0.5-1:0.1-0.5.

[0021] Preferably, the calcination temperature in S4 is 800-1000° C. and the calcination time is 2-4 h.

[0022] The heat and power cogeneration method of waste gasification hydrogen production coupled with SOFC proposed in the present invention adopts the heat and power cogeneration system of waste gasification hydrogen production coupled with SOFC, and the method steps are as follows:

[0023] S1: The garbage is dried by the garbage drying unit, and the garbage hydrogen production unit performs biological fermentation on the kitchen waste to produce hydrogen;

[0024] S2: passing the hydrogen in S1 into a hydrogen purification unit for purification;

[0025] S3: The air and hydrogen purified by S2 are introduced into the SOFC unit to generate electricity. The heat generated by the SOFC unit is used to heat the garbage drying unit through the heat exchange unit.

[0026] Beneficial technical effects of the present invention:

[0027] The present invention uses garbage as raw material, and realizes the heat and power cogeneration of garbage gasification hydrogen production coupled with SOFC through a garbage drying unit, a garbage gasification unit, a garbage purification unit, a SOFC unit and a heat exchange unit, and has good economic benefits and sustainable operation. The present invention uses Sr(NO3)3, butyl titanate and siderite as raw materials, and calcines them under the action of a pore-forming agent, a complexing agent and a structure-directing agent to form an anode skeleton with a unique pore structure, which can form a bonding force with cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate, so that the prepared anode has high stability and fuel utilization rate. In addition, the structure-directing agent of the present invention is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride, which has a synergistic promoting effect on improving the stability and fuel utilization rate of the anode. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a framework diagram of the combined heat and power system of garbage gasification and hydrogen production coupled with SOFC proposed in the present invention. DETAILED DESCRIPTION

[0029] The present invention will be further explained below in conjunction with specific embodiments.

[0030] Reference Figure 1 The waste gasification hydrogen production coupled with SOFC cogeneration system proposed in the present invention comprises:

[0031] A garbage drying unit, used for drying garbage;

[0032] Garbage gasification unit, used for gasification of dried garbage;

[0033] A hydrogen purification unit is used to purify the raw synthesis gas after garbage gasification;

[0034] The SOFC unit generates electricity through air and purified fuel, and the heat generated is used to heat the garbage drying unit through the heat exchange unit.

[0035] In addition, the heat and power cogeneration method of waste gasification hydrogen production coupled with SOFC proposed in the present invention adopts the heat and power cogeneration system of waste gasification hydrogen production coupled with SOFC, and the method steps are as follows:

[0036] S1: The garbage is dried by the garbage drying unit, and the garbage hydrogen production unit performs biological fermentation on the kitchen waste to produce hydrogen;

[0037] S2: passing the hydrogen in S1 into a hydrogen purification unit for purification;

[0038] S3: The air and hydrogen purified by S2 are introduced into the SOFC unit to generate electricity. The heat generated by the SOFC unit is used to heat the garbage drying unit through the heat exchange unit.

[0039] The present invention uses garbage as raw material and realizes heat and power cogeneration of garbage gasification hydrogen production coupled with SOFC through a garbage drying unit, a garbage gasification unit, a garbage purification unit, a SOFC unit and a heat exchange unit, and has good economic benefits and sustainable operation.

[0040] Example 1

[0041] The method steps for preparing the anode of the SOFC unit proposed by the present invention are as follows:

[0042] S1: Sr(NO3)3, butyl titanate, siderite, pore former and complexing agent are dispersed in ethylene glycol to form an anode slurry;

[0043] S2: spraying the anode slurry onto the substrate surface and calcining to obtain the anode skeleton;

[0044] S3: dissolving cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in deionized water to obtain an impregnation solution;

[0045] S4: Immerse the anode skeleton in the impregnation solution, and obtain the anode after calcination.

[0046] The mass ratio of Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent is 1:0.8:0.4::0.15:0.03:0.02.

[0047] In S1, the pore-forming agent is composed of carbon black and polyvinyl alcohol in a mass ratio of 1:0.6; the complexing agent is composed of citric acid and triethanolamine in a mass ratio of 1:1; and the structure-directing agent is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride in a mass ratio of 1:1.

[0048] The calcination temperature in S2 is 1050°C and the time is 4h.

[0049] The mass ratio of cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in S3 is 1:1.2:0.6:0.8:0.3.

[0050] The calcination temperature in S4 is 900°C and the time is 3h.

[0051] Example 2

[0052] The method steps for preparing the anode of the SOFC unit proposed by the present invention are as follows:

[0053] S1: Sr(NO3)3, butyl titanate, siderite, pore former and complexing agent are dispersed in ethylene glycol to form an anode slurry;

[0054] S2: spraying the anode slurry onto the substrate surface and calcining to obtain the anode skeleton;

[0055] S3: dissolving cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in deionized water to obtain an impregnation solution;

[0056] S4: Immerse the anode skeleton in the impregnation solution, and obtain the anode after calcination.

[0057] The mass ratio of Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent is 1:0.5:0.3:0.1:0.01:0.01.

[0058] In S1, the pore-forming agent is composed of carbon black and polyvinyl alcohol in a mass ratio of 1:0.4; the complexing agent is composed of citric acid and triethanolamine in a mass ratio of 3:1; and the structure-directing agent is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride in a mass ratio of 2:1.

[0059] The calcination temperature in S2 is 900°C and the time is 5h.

[0060] The mass ratio of cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in S3 is 1:1:0.5:0.5:0.1.

[0061] The calcination temperature in S4 is 800°C and the time is 4h.

[0062] Example 3

[0063] The method steps for preparing the anode of the SOFC unit proposed by the present invention are as follows:

[0064] S1: Sr(NO3)3, butyl titanate, siderite, pore former and complexing agent are dispersed in ethylene glycol to form an anode slurry;

[0065] S2: spraying the anode slurry onto the substrate surface and calcining to obtain the anode skeleton;

[0066] S3: dissolving cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in deionized water to obtain an impregnation solution;

[0067] S4: Immerse the anode skeleton in the impregnation solution, and obtain the anode after calcination.

[0068] The mass ratio of Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent is 1:1:0.5:0.2:0.05:0.03.

[0069] In S1, the pore-forming agent is composed of carbon black and polyvinyl alcohol in a mass ratio of 1:0.8; the complexing agent is composed of citric acid and triethanolamine in a mass ratio of 1:3; and the structure-directing agent is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride in a mass ratio of 1:2.

[0070] The calcination temperature in S2 is 1200°C and the time is 3h.

[0071] The mass ratio of cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in S3 is 1:1.5:0.8:1:0.5.

[0072] The calcination temperature in S4 is 1000°C and the time is 2h.

[0073] Comparative Example 1

[0074] The structure directing agent of this scheme is hexadecyl (2-acetoxy) dimethyl ammonium chloride, and the other conditions are the same as those in Example 1.

[0075] Comparative Example 2

[0076] The structure directing agent of this scheme is cycloalkyltrimethylammonium chloride, and the other conditions are the same as those in Example 1.

[0077] The fuel utilization and stability of the SOFC unit prepared with the electrodes prepared in Examples 1-3 and Comparative Examples 1-2 were tested on an electrochemical workstation, and the test results are shown in Table 1. Wherein:

[0078] The fuel utilization rate test method is: test temperature 750°C, gas flow rate 120mL / min, and gradually increase the current density until the fuel utilization rate reaches a bottleneck.

[0079] The stability test method is: test temperature 750°C, gas flow rate 120mL / min, and calculate the power density attenuation ratio after working for 2000h at 40% fuel rate.

[0080] Table 1 Electrode performance test results

[0081] Group Fuel utilization rate (%) Power density attenuation ratio (%) Example 1 75 20 Example 2 70 23 Example 3 72 21 Comparative Example 1 58 29 Comparative Example 2 63 32

[0082] It can be seen from the test results in Table 1 that the present invention uses Sr(NO3)3, butyl titanate, siderite and graphene as raw materials, and calcines under the action of pore-forming agent, complexing agent and structure-directing agent to form an anode skeleton with a unique pore structure, which can form a bonding force with cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate, so that the prepared anode has high stability and fuel utilization. In addition, it can be seen from the test records of Example 1 and Comparative Examples 1-2 that the structure-directing agent of the present invention has a great influence on the stability and fuel utilization of the electrode, and the hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride of the present invention have a synergistic effect in improving the stability and fuel utilization of the anode.

Claims

1. A heat and power cogeneration system of garbage gasification hydrogen production coupled with SOFC, characterized in that: include: A garbage drying unit, used for drying garbage; Garbage gasification unit, used for gasification of dried garbage; A hydrogen purification unit is used to purify the raw synthesis gas after garbage gasification; The SOFC unit generates electricity through air and purified fuel, and the heat generated is used to heat the garbage drying unit through the heat exchange unit; The steps of the method for preparing the anode of the SOFC unit are as follows: S1: Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent are dispersed in ethylene glycol to form an anode slurry; S2: spraying the anode slurry onto the substrate surface and calcining to obtain the anode skeleton; S3: dissolving cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in deionized water to obtain an impregnation solution; S4: Immerse the anode skeleton in the impregnation solution, and obtain the anode after calcination.

2. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The mass ratio of Sr(NO3)3, butyl titanate, siderite, pore former, complexing agent and structure directing agent is 1:0.5-1:0.3-0.5:0.1-0.2:0.01-0.05:0.01-0.

03.

3. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The pore former in S1 is composed of carbon black and polyvinyl alcohol in a mass ratio of 1:0.4-0.

8.

4. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The complexing agent in S1 is composed of citric acid and triethanolamine in a mass ratio of 3:1-9.

5. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The structure directing agent in S1 is composed of hexadecyl (2-acetoxy) dimethyl ammonium chloride and cycloalkyl trimethyl ammonium chloride in a mass ratio of 2:1-4.

6. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The calcination temperature in S2 is 900-1200°C and the time is 3-5h.

7. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The mass ratio of cobalt nitrate, nickel nitrate, cerium nitrate, lanthanum nitrate and silver nitrate in S3 is 1:1-1.5:0.5-0.8:0.5-1:0.1-0.

5.

8. The waste gasification hydrogen production coupled with SOFC cogeneration system according to claim 1 is characterized in that: The calcination temperature in S4 is 800-1000°C and the time is 2-4h.

9. A heat and power cogeneration method for waste gasification hydrogen production coupled with SOFC, using the heat and power cogeneration system for waste gasification hydrogen production coupled with SOFC as claimed in any one of claims 1 to 8, characterized in that: The steps are as follows: S1: The garbage is dried by the garbage drying unit, and the garbage hydrogen production unit performs biological fermentation on the kitchen waste to produce hydrogen; S2: passing the hydrogen in S1 into a hydrogen purification unit for purification; S3: The air and hydrogen purified by S2 are introduced into the SOFC unit to generate electricity. The heat generated by the SOFC unit is used to heat the garbage drying unit through the heat exchange unit.

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