CN111086987A - Method for preparing activated carbon and co-producing hydrogen from animal excrement - Google Patents
Method for preparing activated carbon and co-producing hydrogen from animal excrement Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 241001465754 Metazoa Species 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- 230000004913 activation Effects 0.000 claims abstract description 60
- 230000008569 process Effects 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012071 phase Substances 0.000 claims abstract description 29
- 238000000197 pyrolysis Methods 0.000 claims abstract description 28
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 210000003608 fece Anatomy 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 241000287828 Gallus gallus Species 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001994 activation Methods 0.000 abstract description 56
- 239000002994 raw material Substances 0.000 abstract description 13
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002551 biofuel Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 20
- 238000002791 soaking Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000004093 laser heating Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052908 analcime Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a process method for preparing activated carbon and co-producing hydrogen by using animal excrement, which comprises the following steps: pyrolyzing animal excrement to obtain a first gas-phase material and a first solid-phase material, and allowing the first gas-phase material to enter a second reaction unit for reaction to obtain a second gas-phase material and a second solid-phase material; the second gas-phase material enters a third reaction unit to react to obtain a third gas-phase material and a third solid-phase material, and the third gas-phase material is condensed and separated to obtain water and carbon dioxide gas; and (3) carrying out contact reaction on the second solid-phase material and steam to obtain hydrogen, carrying out pretreatment and activation treatment on the first solid-phase material, cooling, and carrying out acid washing, water washing and drying in sequence to obtain the activated carbon. The method organically combines the pyrolysis process of the raw materials and the activation process after carbonization, thereby greatly improving the utilization rate of the biofuel while avoiding further environmental pollution.
Description
Technical Field
The invention relates to the technical field of renewable energy utilization, in particular to a process method for preparing activated carbon and co-producing hydrogen from animal excrement.
Background
With the rapid development of the dairy livestock industry, the production of a large amount of animal excrement can cause serious environmental pollution, and therefore, the breeding of mosquitoes and flies can cause great harm to the health of human bodies. Contamination by animal excrement has become a leading problem currently restricting the development of the dairy industry. At present, the traditional treatment method for animal excrement mainly comprises the modes of fertilizer, energy and the like. The cow dung has large food intake and high output, so that the cow dung can be used as an animal organic fertilizer for mass production. However, because of its compact texture and high water content, the slow rate of decomposition tends to slow the fertilizer efficiency; in a few regions which are not reached in China, particularly in pasturing areas, cow dung is often used as a living fuel to be directly combusted for cooking and heating, but a large amount of harmful gas is generated to pollute the environment. Although the existing method for producing biogas by using cow dung through drying and fermentation still has the problem of low energy utilization rate, the generated waste needs to be subjected to secondary treatment, so that the cost for producing biogas is increased.
CN104003386A discloses a method for preparing powdered activated carbon by taking cow dung as a raw material, which comprises the steps of drying the cow dung, mixing and soaking the dried cow dung with a phosphoric acid and potassium dihydrogen phosphate composite activating agent, carrying out combustion carbonization for 1-3 hours at 400-800 ℃ under an anaerobic condition, finally washing the cow dung to be neutral by distilled water, and drying the cow dung to obtain the powdered activated carbon. The method adopts a composite activation method to realize the reutilization of the cow dung waste, but has the problem of higher cost of the composite activator.
CN101914573A discloses a method for preparing hydrogen and methane step by anaerobic fermentation of cow dung, which comprises adjusting pH by chemical pretreatment method, purging with nitrogen to remove oxygen, and fermenting hydrogen microorganism under anaerobic condition to prepare hydrogen. After the hydrogen fermentation is finished, adjusting the pH to 7 by using potassium hydroxide, and acclimating the anaerobic activated sludge to prepare the biomass methane gas. The method has high utilization rate of raw materials and high fermentation benefit. But the purity of the prepared biomass hydrogen is low, and the requirement of industrial application is difficult to meet.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a process method for preparing activated carbon and co-producing hydrogen from animal excrement. The method organically combines the pyrolysis process of the raw materials and the activation process after carbonization, greatly improves the utilization rate of the biofuel while avoiding further environmental pollution, and obtains high-purity hydrogen. The physicochemical activating agent involved in the method and the reactant in the hydrogen production process can be recycled, so that the process cost is reduced, the product quality is improved, and the method has a wide development prospect.
The invention provides a process method for preparing activated carbon and co-producing hydrogen by using animal excrement, which comprises the following steps:
(1) the first pyrolysis reaction unit is used for receiving and pyrolyzing animal excrement to obtain a first gas-phase material and a first solid-phase material after reaction;
(2) the second reaction unit is used for receiving and processing the first gas-phase material, and the first gas-phase material is contacted with the ferric oxide in the second reaction unit and reacts to obtain a second gas-phase material and a second solid-phase material;
(3) the third reaction unit is used for receiving and processing a second gas-phase material, the second gas-phase material is contacted with nickel oxide in the third reaction unit and reacts to obtain a third gas-phase material and a third solid-phase material after reaction, and water and carbon dioxide gas are obtained after the third gas-phase material is condensed and separated;
(4) contacting the second solid-phase material with water vapor and reacting to obtain hydrogen;
(5) and mixing the first solid-phase material with a first activating agent for activation pretreatment, then carrying out first activation treatment, cooling after the first activation treatment is finished, and then carrying out acid washing, water washing and drying in sequence to obtain the activated carbon.
In the process method, the animal excrement is one or more of cow dung, pig dung, sheep dung and chicken dung, and preferably cow dung.
In the process method, animal excrement is dehydrated before entering the first pyrolysis reaction unit, and the water content of the treated animal excrement is not more than 15 wt%. Further preferably, the animal excrement obtained by the dehydration treatment is ground, and the ground material is 20 to 80 meshes in size.
In the process method, the pyrolysis temperature in the first pyrolysis reaction unit is 600-1000 ℃, the pyrolysis time is 1-3 hours, the pyrolysis is carried out in nitrogen or inert atmosphere, and the inert atmosphere can be one or more of helium, neon, argon, krypton and xenon. The first pyrolysis reaction unit can be heated by any one of the existing heating modes, such as one or more of electric heating, microwave heating, plasma heating, laser heating and electron beam heating, preferably by a microwave heating mode, and when the microwave heating mode is adopted, the microwave power density is 2000-3000W/kg.
In the process method of the invention, the first gas phase material is CO and H2、CO2、CH4And a small amount of olefin, and CO and CH in the mixed gas4And H2Will react with Fe filled in the second reaction unit2O3Reaction to form Fe3O4、CO2And steam, Fe produced3O4Will continue to react with the unreacted CO, CH in the mixed gas4And H2To generate Fe, FeO and CO2And water vapor. The second solid phase material is Fe and FeO after the reaction.
In the process of the invention, the second gaseous feed comprises the CO produced2The second gas phase material is introduced into a third reaction unit containing NiO, and further CO and CH in the third reaction unit4And H2Conversion to CO2And water vapor.
In the process method, the second reaction unit and the third reaction unit can be one or more of a fixed bed reactor and a fluidized bed reactor, and are preferably fixed bed reactors. The second reaction unit and the third reaction unit can be in a fixed bed reactor, or can be respectively independent of different reactors, preferably respectively independent of different reactors.
In the process of the invention, the second reaction unit can be provided with more than one fixed bed reactor, when more than two fixed bed reactors are provided, more than two fixed bed reactors can be connected in parallel and/or in series, more preferably in parallel, the reactors are operated alternately, and when one reactor is regenerated, the other reactor is started.
In the process of the present invention, the third reaction unit may be provided with more than one fixed bed reactor, when more than two fixed bed reactors are provided, the more than two fixed bed reactors may be connected in parallel and/or in series, more preferably in parallel, the reactors are operated alternately, and when one reactor is regenerated, the other reactor is started.
In the process method, the reaction temperature of the second reaction unit is 800-1000 ℃, the reaction residence time is 10-30 mi, and the reactor is filled with excessive Fe2O3。
In the process method, the reaction temperature of the third reaction unit is 800-1000 ℃, the reaction residence time is 10-30 min, and the reactor is filled with excessive NiO.
In the process method, the reaction temperature of the steam and the second solid-phase material in the step (4) is 600-800 ℃. The water vapor in the step (4) can be prepared into water vapor through heating, vaporizing and converting the water condensed and separated in the step (3).
In the process method, after the first activation treatment in the step (5) is finished, the temperature is reduced to 20-30 ℃.
In the process method, the acid washing in the step (5) is to mix the activated material with an acid solution, and the acid solution is hydrochloric acid. The concentration of the acid solution is 0.1-1 mol/L. The water wash was water to neutral (pH = 7). The drying is carried out for 8-12 h at the temperature of 100-110 ℃.
In the process of the invention, the first activating agent can be one or more of zinc chloride, potassium hydroxide, phosphoric acid, sodium hydroxide and sodium carbonate, and is preferably zinc chloride. The mass ratio of the first solid phase material to the first activating agent is 1:0.5 to 3. The activation pretreatment is preferably carried out under the ultrasonic condition, and the activation pretreatment time is 20-30 min.
In the process method, the first activation treatment temperature is 400-600 ℃, and the activation time is 1-2 hours; the first activation treatment is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere can be one or more of helium, neon, argon, krypton and xenon. The first pyrolysis reaction unit can be heated by any one of the existing heating modes, such as one or more of electric heating, microwave heating, plasma heating, laser heating and electron beam heating, preferably by a microwave heating mode, and when the microwave heating mode is adopted, the microwave power density is 2000-3000W/kg.
In the process method, the activated carbon obtained after drying in the step (5) can be subjected to second activation treatment, carbon dioxide gas is introduced during the second activation treatment, the flow rate of the carbon dioxide gas is controlled to be 50-150 mL/min, and the carbon dioxide obtained in the step (3) is preferably used. The second activation treatment temperature is 800-1000 ℃, and the activation time is 1-2 h; the second activation treatment can be carried out by any one of the existing heating modes, such as one or more of electric heating, microwave heating, plasma heating, laser heating and electron beam heating, preferably by the microwave heating mode, and when the microwave heating mode is adopted, the microwave power density is 2000-3000W/kg.
In the process method, the purity of the hydrogen obtained in the step (4) is more than 95 percent.
In the process method of the invention, the specific surface area of the activated carbon obtained in the step (6) is more than 1000 m2Iodine adsorption value of more than 800mg/g, and preferably specific surface area of more than 1500 m2The iodine adsorption value is more than 1200 mg/g.
Compared with the prior art, the process method for preparing the activated carbon and co-producing the hydrogen by using the animal excrement has the following advantages:
1. the process method organically combines the process of preparing the active carbon by pyrolyzing the raw materials with the process of separating and purifying the mixed gas generated by pyrolyzing the raw materials, and separates the mixed gas to obtain CO2When the method is used for preparing the activated carbon, the activated carbon with a specific structure and high-purity hydrogen are obtained, the property of the activated carbon is improved, and the activation cost is reduced. The problem of low resource utilization rate of biological raw materials in the prior art is solved, the mixed gas generated in the animal excrement pyrolysis process is fully utilized, the pollutant emission is reduced, and the maximum utilization of the raw materials is realized.
2. In the process of preparing the activated carbon, the activated carbon obtained by the process method has large specific surface area and high mesoporous occupation ratio under the combined action of three modes of pretreatment, first activation treatment and second activation treatment. The method comprises the steps of firstly utilizing ultrasonic waves to pretreat biological coke, reducing the crystallinity of the biological coke, enabling the structure to be loose and beneficial to subsequent activation, enabling the first activation treatment to be more beneficial to preparing activated carbon with high specific surface area and developed micropores, enabling the second activation treatment to further regulate and control the pore structure of the activated carbon on the basis of the first activation treatment and increase the distribution of mesopores, and enabling the prepared activated carbon to have high specific surface area and simultaneously contain a large number of mesopores and micropore structures.
3. In the process method, the second reaction unit and the third reaction unit are arranged, the reaction of Fe, FeO and water vapor is reasonably utilized, the purity of the hydrogen is improved, the purity of the hydrogen is over 95 percent, and the problem of low hydrogen purity in the prior art for preparing hydrogen from animal excreta is solved. And a second reaction unitFe used2O3NiO used in the third reaction unit can be recycled.
Detailed Description
The synthesis of the analcime of the present invention is described in detail below by way of specific examples, but is not limited thereto.
In the examples of the present invention and the comparative examples: the pyrolysis reaction unit adopts a microwave reactor, the second reaction unit and the third reaction unit are independent fixed bed reactors respectively, wherein the second reaction unit comprises two fixed bed reactors which are operated alternately, and when one of the fixed bed reactors needs to be regenerated, the other fixed bed reactor is started. The third reaction unit comprises two fixed bed reactors, the two fixed bed reactors are operated alternately, and when one fixed bed reactor needs to be regenerated, the other fixed bed reactor is started.
Example 1
(1) 20g of cow dung raw material was weighed and dried at 105 ℃ for 12 hours. Taking out, grinding, sieving to obtain 40-mesh dry cow dung powder, putting into a microwave reactor, and pyrolyzing for 2h at 800 ℃ and 2000W/kg microwave power density in nitrogen atmosphere;
(2) the mixed gas generated by the pyrolysis in the step (1) enters a reactor in a second reaction unit, and 100gFe is filled in the reactor2O3Controlling the reaction temperature of the reactor to be 900 ℃ and the reaction retention time to be 10 min;
(3) the gas obtained after the reaction in the step (2) enters a third reaction unit, 100g of NiO is filled in the reactor, the reaction temperature of the reactor is controlled to be 900 ℃, the reaction residence time is 10min, and the gas phase obtained by the reaction is condensed at 0 ℃ to obtain high-purity CO2And water;
(4) when the reactor of the second reaction unit in the step (2) needs to be regenerated, switching the reactors, and introducing steam into the first reactor, wherein the reaction temperature is 650 ℃, so as to obtain high-purity hydrogen, and the purity of the high-purity hydrogen is 97.3%;
(5) the biological coke and ZnCl obtained after the pyrolysis in the step (1)2Soaking the solution in the same volume at a soaking ratio of1:2, pretreating in an ultrasonic cleaning machine for 20min, putting the pretreated product into a microwave reactor to perform first activation treatment in a nitrogen atmosphere, wherein the microwave power density is 2000W/kg, the activation temperature is 500 ℃, the activation time is 1h, then after the temperature is reduced to 30 ℃, washing with 1L of 0.1mol/L hydrochloric acid, then washing with water until the pH value is 7, and drying at 105 ℃ for 12h to obtain activated carbon; the BET specific surface area is 1332m2The iodine adsorption value is 855 mg/g.
Example 2
(1) 20g of cow dung raw material was weighed and dried at 105 ℃ for 12 hours. Taking out, grinding and screening to 40 meshes, putting the dried cow dung powder into a microwave reactor, and pyrolyzing for 2 hours at 800 ℃ and 2000W/kg microwave power density in nitrogen atmosphere;
(2) the mixed gas generated by the pyrolysis in the step (1) enters a reactor in a second reaction unit, and 100gFe is filled in the reactor2O3Controlling the reaction temperature of the reactor to be 900 ℃ and the reaction retention time to be 10 min;
(3) the gas obtained after the reaction in the step (2) enters a third reaction unit, 100g of NiO is filled in the reactor, the reaction temperature of the reactor is controlled to be 900 ℃, the reaction residence time is 10min, and the gas phase obtained after the reaction is condensed at 0 ℃ to obtain high-purity CO2And water;
(4) when the reactor of the second reaction unit in the step (2) needs to be regenerated, switching the reactors, and introducing steam into the first reactor, wherein the reaction temperature is 650 ℃, so as to obtain high-purity hydrogen, and the purity of the high-purity hydrogen is 97.4%;
(5) the biological coke and ZnCl obtained after the pyrolysis in the step (1)2Soaking the solution in the same volume at a soaking ratio of 1:2, then pretreating in an ultrasonic cleaning machine for 20min, after the pretreatment is finished, putting the pretreated solution into a microwave reactor to perform first activation treatment in a nitrogen atmosphere, wherein the microwave power density is 2000W/kg, the activation temperature is 500 ℃, the activation time is 1h, then after the temperature is reduced to 30 ℃, carrying out acid cleaning by using 1L of 0.1mol/L hydrochloric acid, then washing with water until the pH value is 7, and drying at 105 ℃ for 12h to obtain activated carbon;
(6) taking out the section of activated carbon dried in the step (5) and putting the section of activated carbon into microwaveCarrying out secondary activation in the reactor, and introducing CO generated in the step (2) for secondary activation2The activation temperature is 900 ℃, the microwave power density is 2000W/kg, the activation time is 1h, and finally the activated carbon product is obtained, wherein the BET specific surface area is 1521m2The iodine adsorption value was 1311 mg/g.
Example 3
1) 20g of cow dung raw material was weighed and dried at 105 ℃ for 12 hours. Taking out, grinding and screening to 20 meshes, putting the dried cow dung powder into a microwave reactor, and pyrolyzing for 1h at 600 ℃ and 2000W/kg microwave power density in nitrogen atmosphere;
(2) the mixed gas generated by the pyrolysis in the step (1) enters a reactor in a second reaction unit, and 100gFe is filled in the reactor2O3Controlling the reaction temperature of the reactor to be 800 ℃ and the reaction retention time to be 10 min;
(3) the gas obtained after the reaction in the step (2) enters a third reaction unit, 100g of NiO is filled in the reactor, the reaction temperature of the reactor is controlled to be 800 ℃, the reaction residence time is 10min, and the gas phase obtained after the reaction is condensed at 0 ℃ to obtain high-purity CO2And water;
(4) when the reactor of the second reaction unit in the step (2) needs to be regenerated, switching the reactors, and introducing steam into the first reactor, wherein the reaction temperature is 600 ℃, so as to obtain high-purity hydrogen, and the purity of the high-purity hydrogen is 95.4%;
(5) the biological coke and ZnCl obtained after the pyrolysis in the step (1)2Soaking the solution in the same volume, wherein the soaking ratio is 1:0.5, then pretreating in an ultrasonic cleaning machine for 20min, after the pretreatment is finished, putting the pretreated solution into a microwave reactor to perform first activation treatment in a nitrogen atmosphere, wherein the microwave power density is 2000W/kg, the activation temperature is 400 ℃, the activation time is 1h, then after the temperature is reduced to 30 ℃, pickling with 1L of 0.1mol/L hydrochloric acid, then washing with water until the pH value is 7, and drying at 105 ℃ for 12h to obtain activated carbon;
(6) taking out the dried first-stage activated carbon, putting the dried first-stage activated carbon into a microwave reactor for second-stage activation, and introducing CO generated in the step (2) into the second-stage activation2The activation temperature is 800 ℃, the microwave power density is 2000W/kg, the activation time is 1h,finally obtaining the activated carbon product with the BET specific surface area of 1176m2(ii)/g, iodine adsorption value is 1086 mg/g.
Example 4
1) 20g of cow dung raw material was weighed and dried at 105 ℃ for 12 hours. Taking out, grinding and screening to 80 meshes, putting the dried cow dung powder into a microwave reactor, and pyrolyzing for 3 hours at 1000 ℃ and 3000W/kg microwave power density in nitrogen atmosphere;
(2) the mixed gas generated by the pyrolysis in the step (1) enters a reactor in a second reaction unit, and 100gFe is filled in the reactor2O3Controlling the reaction temperature of the reactor to be 1000 ℃ and the reaction retention time to be 10 min;
(3) the gas obtained after the reaction in the step (2) enters a third reaction unit, 100g of NiO is filled in the reactor, the reaction temperature of the reactor is controlled to be 1000 ℃, the reaction residence time is 10min, and the gas phase obtained after the reaction is condensed at 0 ℃ to obtain high-purity CO2And water;
(4) when the reactor of the second reaction unit in the step (2) needs to be regenerated, switching the reactors, and introducing steam into the first reactor, wherein the reaction temperature is 800 ℃, so as to obtain high-purity hydrogen, and the purity of the high-purity hydrogen is 96.2%;
(5) the biological coke and ZnCl obtained after the pyrolysis in the step (1)2Soaking the solution in the same volume at a soaking ratio of 1:3, then pretreating in an ultrasonic cleaning machine for 20min, after the pretreatment is finished, putting the pretreated solution into a microwave reactor to perform first activation treatment in a nitrogen atmosphere, wherein the microwave power density is 3000W/kg, the activation temperature is 600 ℃, the activation time is 2h, then after the temperature is reduced to 30 ℃, carrying out acid cleaning by using 1L of 0.1mol/L hydrochloric acid, then washing with water until the pH value is 7, and drying at 105 ℃ for 12h to obtain activated carbon;
(6) taking out the dried first-stage activated carbon, putting the dried first-stage activated carbon into a microwave reactor for second-stage activation, and introducing CO generated in the step (2) into the second-stage activation2The activation temperature is 800 ℃, the microwave power density is 3000W/kg, the activation time is 2h, and finally the activated carbon product is obtained, wherein the BET specific surface area is 1483m2(ii)/g, iodine adsorption value is 1217 mg/g.
Example 5
1) 20g of cow dung raw material was weighed and dried at 105 ℃ for 12 hours. Taking out, grinding and screening to 30 meshes, putting the dried cow dung powder into a microwave reactor, and pyrolyzing for 2 hours at 900 ℃ and 2500W/kg microwave power density in nitrogen atmosphere;
(2) the mixed gas generated by the pyrolysis in the step (1) enters a reactor in a second reaction unit, and 100gFe is filled in the reactor2O3Controlling the reaction temperature of the reactor to be 850 ℃ and the reaction retention time to be 10 min;
(3) the gas obtained after the reaction in the step (2) enters a third reaction unit, 100g of NiO is filled in the reactor, the reaction temperature of the reactor is controlled to be 850 ℃, the reaction retention time is 10min, and the gas phase obtained after the reaction is condensed at 0 ℃ to obtain high-purity CO2And water;
(4) when the reactor of the second reaction unit in the step (2) needs to be regenerated, switching the reactors, and introducing steam into the first reactor, wherein the reaction temperature is 700 ℃, so as to obtain high-purity hydrogen, and the purity of the high-purity hydrogen is 97.1%;
(5) the biological coke and ZnCl obtained after the pyrolysis in the step (1)2Soaking the solution in the same volume at a soaking ratio of 1:2, then pretreating in an ultrasonic cleaning machine for 30min, after the pretreatment is finished, putting the pretreated solution into a microwave reactor to perform first activation treatment in a nitrogen atmosphere, wherein the microwave power density is 2500W/kg, the activation temperature is 550 ℃, the activation time is 1.5h, then after the temperature is reduced to 30 ℃, washing the solution with 1L of 0.1mol/L hydrochloric acid, then washing the solution with water until the pH value is 7, and drying the solution at 110 ℃ for 8h to obtain activated carbon;
(6) taking out the dried first-stage activated carbon, putting the dried first-stage activated carbon into a microwave reactor for second-stage activation, and introducing CO generated in the step (2) into the second-stage activation2The activation temperature is 800 ℃, the microwave power density is 2500W/kg, the activation time is 1.5h, and finally the activated carbon product is obtained, and the BET specific surface area is 1648m2The iodine adsorption value is 1395 mg/g.
Claims (18)
1. A process method for preparing activated carbon and co-producing hydrogen from animal excrement comprises the following steps:
(1) the first pyrolysis reaction unit is used for receiving and pyrolyzing animal excrement to obtain a first gas-phase material and a first solid-phase material after reaction;
(2) the second reaction unit is used for receiving and processing the first gas-phase material, and the first gas-phase material is contacted with the ferric oxide in the second reaction unit and reacts to obtain a second gas-phase material and a second solid-phase material;
(3) the third reaction unit is used for receiving and processing a second gas-phase material, the second gas-phase material is contacted with nickel oxide in the third reaction unit and reacts to obtain a third gas-phase material and a third solid-phase material after reaction, and water and carbon dioxide gas are obtained after the third gas-phase material is condensed and separated;
(4) contacting the second solid-phase material with water vapor and reacting to obtain hydrogen;
(5) and mixing the first solid-phase material with an activating agent for pretreatment, then carrying out first activation treatment, cooling after the first activation treatment is finished, and then carrying out acid washing, water washing and drying in sequence to obtain the activated carbon.
2. A process according to claim 1, characterized in that: the animal excrement is one or more of cow dung, pig dung, sheep dung and chicken dung, and preferably cow dung.
3. A process according to claim 1, characterized in that: the animal excrement is dehydrated before entering the first pyrolysis reaction unit, and the water content of the treated animal excrement is not more than 15 wt%.
4. A process according to claim 1, characterized in that: the pyrolysis temperature in the first pyrolysis reaction unit is 600-1000 ℃, and the pyrolysis time is 1-3 h.
5. A process according to claim 1 or 4, characterized in that: the pyrolysis is carried out in nitrogen or inert atmosphere, and the inert atmosphere is one or more of helium, neon, argon, krypton and xenon.
6. A process according to claim 1, characterized in that: the second reaction unit and the third reaction unit are one or more of a fixed bed reactor and a fluidized bed reactor, and preferably are fixed bed reactors.
7. A process according to claim 1, characterized in that: the second reaction unit and the third reaction unit are in one reactor, or are respectively independent of different reactors, preferably are respectively independent of different reactors.
8. A process according to claim 1, characterized in that: the reaction temperature of the second reaction unit is 800-1000 ℃.
9. A process according to claim 1, characterized in that: the reaction temperature of the third reaction unit is 800-1000 ℃.
10. A process according to claim 1, characterized in that: and (4) the reaction temperature of the steam and the second solid-phase material in the step (4) is 600-800 ℃.
11. A process according to claim 1, characterized in that: and (5) carrying out pretreatment under an ultrasonic condition for 20-30 min.
12. A process according to claim 1, characterized in that: the activating agent in the step (5) is one or more of zinc chloride, potassium hydroxide, phosphoric acid, sodium hydroxide and sodium carbonate, and preferably zinc chloride.
13. A process according to claim 1, characterized in that: the mass ratio of the first solid phase material to the activating agent in the step (5) is 1:0.5 to 3.
14. A process according to claim 1, characterized in that: the first activation treatment temperature in the step (5) is 400-600 ℃, and the activation time is 1-2 h; the first activation treatment is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one or more of helium, neon, argon, krypton and xenon.
15. A process according to claim 1, characterized in that: and (5) cooling to 20-30 ℃ after the first activation treatment in the step (5) is finished.
16. A process according to claim 1, characterized in that: and (5) acid washing is to mix the activated material with an acid solution, wherein the acid solution is hydrochloric acid, and the concentration of the acid solution is 0.1-1 mol/L.
17. A process according to claim 1, characterized in that: and (5) carrying out second activation treatment on the dried activated carbon, wherein carbon dioxide gas is introduced during the second activation treatment, the temperature of the second activation treatment is 800-1000 ℃, and the activation time is 1-2 h.
18. The process of claim 17 wherein: and (4) adopting the carbon dioxide obtained in the step (3) as the carbon dioxide.
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| GB1372292A (en) * | 1971-02-02 | 1974-10-30 | Basf Ag | Production of carbon by eliminating hydrogen chloride from poly vinylidene chloride |
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