CN110586109A - Catalyst for catalyzing cracking of solid combustible gasified tar - Google Patents
Catalyst for catalyzing cracking of solid combustible gasified tar Download PDFInfo
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- CN110586109A CN110586109A CN201910857392.6A CN201910857392A CN110586109A CN 110586109 A CN110586109 A CN 110586109A CN 201910857392 A CN201910857392 A CN 201910857392A CN 110586109 A CN110586109 A CN 110586109A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000007787 solid Substances 0.000 title claims abstract description 29
- 238000005336 cracking Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000002893 slag Substances 0.000 claims abstract description 92
- 238000003723 Smelting Methods 0.000 claims abstract description 79
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000002309 gasification Methods 0.000 claims abstract description 26
- 150000002815 nickel Chemical class 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052611 pyroxene Inorganic materials 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for catalyzing the cracking of gasified tar of solid combustible, belonging to the technical field of energy and environment; the catalyst is nickel smelting slag generated in various nickel smelting processes and technological processes such as nickel flash smelting slag, converter slag, ore thermoelectric furnace slag and the like; or activated nickel smelting slag, wherein the nickel smelting slag can be calcined and activated in the atmosphere of air, oxygen-enriched air, pure oxygen or water vapor after being crushed, screened and dried, reduced and activated in the atmosphere of a mixture of reducing gas and inert gas, and activated in the atmosphere of combustible gas generated by gasification of solid combustible substances, so that activated nickel smelting slag is obtained; the method realizes resource utilization of the nickel smelting slag, the prepared nickel smelting slag catalyst has stable property, good safety and high mechanical strength, can obviously reduce the preparation and use cost of the tar cracking catalyst, provides a cheap catalyst for catalytic cracking of solid combustible gasified tar, and has better economic benefit and environmental benefit.
Description
Technical Field
The invention relates to a nickel smelting slag catalyst for catalyzing the pyrolysis of solid combustible gasified tar and an activation method thereof, belonging to the technical field of energy and environment.
Background
At present, the method for resource utilization of solid combustible mainly comprises direct combustion, pyrolysis, gasification and the like. Gasification is a process in which solid combustible is thermochemically treated to produce a combustible gas, the main component of which is H2、CO、CH4、CO2And N2And the like. The gasification treatment of the solid combustible can improve the utilization efficiency of resources and reduce the emission of pollutants, and has obvious advantages compared with incineration. The high-grade fuel gas generated by gasifying the solid combustible can be directly used as fuel, and can also be further synthesized into liquid fuel or used for producing other chemicals.
In the gasification of solid combustibles, tar is an inevitable by-product. The tar is a dark brown viscous liquid, has complex components, and contains benzene derivatives, polycyclic aromatic hydrocarbons, heterocyclic compounds, asphaltenes and the like. The presence of tar has a number of detrimental effects on the gasification process of solid combustible materials and the utilization of the gasified fuel gas. Tar is gaseous at high temperatures and condenses to a liquid at low temperatures (< 300 ℃), which makes handling and separation extremely difficult. Among various methods for tar conversion or removal, catalytic cracking has a high tar conversion rate and a relatively low catalytic cracking temperature, and is considered to be the most advanced and effective tar removal method at present.
The catalyst commonly used for cracking the solid combustible gasified tar mainly comprises natural ore catalyst (limestone, dolomite, olivine, etc.), nickel-based catalyst and noble metal catalyst. The natural ore catalyst generally has the defects of low tar conversion rate, easy abrasion and the like; the nickel-based catalyst has high tar conversion rate, but has the problem of rapid inactivation, and the waste nickel-based catalyst is difficult to treat due to the toxicity; the noble metal catalyst has good catalytic effect, but the expensive price limits the application of the noble metal catalyst in industry, so the development of the solid combustible gasification tar cracking catalyst with high mechanical strength, good catalytic effect and low price is necessary.
The nickel smelting slag is an industrial waste slag discharged in the nickel pyrometallurgical process, is a byproduct of the nickel smelting process, mainly comprises olivine, magnetite, pyroxene and other valuable metals, and also contains nickel, copper and the like, wherein the content of iron is more than 20 percent, the nickel mainly exists in the states of sulfide and a small amount of metal alloy, the quantity of the nickel smelting slag generated in each year in China is huge, according to investigation, about 6 ~ 20 tons of slag are generated when 1 ton of nickel is produced, the discharge or the stacking of the nickel smelting slag not only causes serious environmental pollution, but also causes the waste of a large amount of valuable metals, and how to realize the resource utilization of the nickel smelting slag is a prominent problem facing at present.
Disclosure of Invention
The invention aims to provide a catalyst for catalyzing the gasification and tar cracking of solid combustible materials, which has low price, high mechanical strength and good catalytic effect, aiming at the problems and the defects in the prior art; the catalyst is nickel smelting slag generated in nickel smelting processes and technological processes such as nickel flash smelting slag, converter slag, ore thermoelectric furnace slag and the like, the main phases of the catalyst are olivine, magnetite, pyroxene and a small amount of sulfides and oxides of nickel and copper, and the main chemical components of the catalyst are Fe: 25 to 42% of SiO2: 30-45%, CaO: 5-10%, MgO: 5-10%, Ni: 0.1-0.3%, Cu: 0.1 to 0.2 percent. The method utilizes the nickel smelting slag to catalyze the cracking of the gasified tar of the solid combustible, prepares high-quality combustible gas through the catalytic gasification of the solid combustible, and promotes the resource utilization of the solid combustible and the nickel smelting slag.
The catalyst can also be activated nickel smelting slag, and the activation method of the nickel smelting slag is selected from one of the following methods:
A. method 1
(1) Crushing the nickel smelting slag, screening to obtain particles with the particle size of 20 ~ 40 meshes, and then drying for 5 ~ 24h at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and calcining the dried nickel smelting slag for 5 ~ 20 hours at the temperature of 750 ~ 1050 ℃ in the atmosphere of air, oxygen-enriched oxygen, pure oxygen or steam to obtain the activated nickel smelting slag.
B. Method two
(1) Crushing the nickel smelting slag, screening to obtain particles with the particle size of 20 ~ 40 meshes, and then drying for 5 ~ 24h at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and (2) loading the dried nickel smelting slag into a catalyst activation reactor, introducing a mixture of reducing gas and inert gas, wherein the volume percentage of the reducing gas is 5 ~ 100% and reducing for 1 ~ 8h at 650 ~ 950 ℃ to obtain the activated nickel smelting slag.
The reducing gas includes, but is not limited to, hydrogen, carbon monoxide and methane, and the inert gas includes, but is not limited to, nitrogen, helium and argon.
C. Method III
(1) Crushing the nickel smelting slag, screening out particles with the particle size of 20 ~ 40 meshes, and then drying the particles for 5 ~ 24 hours at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and (3) putting the dry nickel smelting slag into a catalyst activation reactor, introducing combustible gas generated by gasification of solid combustible, and treating for 3 ~ 24h at the reaction temperature of 700-1000 ℃ to obtain the activated nickel smelting slag.
The invention has the beneficial effects that: (1) the resource utilization of the nickel smelting slag is realized, the nickel smelting slag does not contain toxic and harmful easily-soluble components after high-temperature activation treatment, and the nickel smelting slag has stable property, good safety and high mechanical strength;
(2) the nickel smelting slag or the activated nickel smelting slag is used as a catalyst for catalyzing the pyrolysis of the solid combustible gasified tar, so that the preparation and use cost of the tar pyrolysis catalyst can be reduced, a cheap catalyst is provided for the catalytic pyrolysis of the solid combustible gasified tar, and the catalyst has good economic benefit and environmental benefit;
(3) the nickel smelting slag catalyst can be repeatedly used and regenerated, and can still keep higher catalytic activity after regeneration, and the total catalytic life is long. The waste nickel smelting slag catalyst can be safely utilized as resources, and is used for cement raw materials or building materials and the like.
Detailed Description
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the invention.
Example 1: the nickel flash smelting slag of the catalyst of the embodiment comprises the following components: 39.20% of SiO2：33.50%，CaO：2.40%，MgO：7.90%，Ni：0.26%，Cu：0.16%。
The catalyst of the embodiment is used for catalyzing the gasification and tar cracking of municipal solid waste, the catalyst is placed in a fixed bed reactor, tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:1, and the tar conversion rate is 38% when the catalytic cracking reaction temperature is 800 ℃.
Example 2: the catalyst of the embodiment is activated nickel flash smelting slag, wherein the nickel flash smelting slag comprises the following components: 39.20% of SiO2: 33.50%, CaO: 2.40%, MgO: 7.90%, Ni: 0.26%, Cu: 0.16%, the activation method is as follows:
(1) putting the nickel flash smelting slag into a crusher for crushing, sieving to obtain particles with the particle size of 20 meshes, and drying at the temperature of 105 ℃ for 12 hours to remove moisture;
(2) and calcining the dried nickel flash smelting slag for 5 hours at the temperature of 1000 ℃ in the air atmosphere to obtain the activated nickel smelting slag catalyst.
The activated nickel flash smelting slag is used for catalyzing the gasification and tar cracking of municipal solid waste, the catalyst is placed in a fixed bed reactor, tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:1, and when the catalytic cracking reaction temperature is 800 ℃, the tar conversion rate is 74%.
Example 3: the catalyst of the embodiment is activated nickel flash smelting slag, wherein the nickel flash smelting slag comprises the following components: 39.20% of SiO2: 33.50%, CaO: 2.40%, MgO: 7.90%, Ni: 0.26%, Cu: 0.16%, the activation method is as follows:
(1) putting the nickel flash smelting slag into a crusher for crushing, screening out particles with the granularity of 40 meshes, and drying for 24 hours at the temperature of 150 ℃ to remove moisture;
(2) loading the dried nickel flash smelting slag into a catalyst activation reactor, introducing mixed gas of hydrogen and nitrogen, wherein the volume percentage of the hydrogen is 50%, and reducing for 6 hours at the temperature of 900 ℃ to obtain an activated nickel smelting slag catalyst;
the activated nickel flash smelting slag is used for catalyzing the gasification and tar cracking of municipal solid waste, the catalyst is placed in a fixed bed reactor, tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:1, and the tar conversion rate is 65% when the catalytic cracking reaction temperature is 800 ℃.
Example 4: the catalyst of this example was activated nickel flash smelting slag, in whichThe nickel flash smelting slag comprises the following components: 39.20% of SiO2: 33.50%, CaO: 2.40%, MgO: 7.90%, Ni: 0.26%, Cu: 0.16%, the activation method is as follows:
(1) putting the nickel flash smelting slag into a crusher for crushing, screening out particles with the particle size of 30 meshes, and then drying for 20 hours at the temperature of 110 ℃ to remove moisture;
(2) loading the dried nickel flash smelting slag into a catalyst activation reactor, introducing combustible gas generated by gasifying pine nut shells into the reactor, wherein the main components of the combustible gas are hydrogen, carbon monoxide, methane, carbon dioxide, nitrogen and the like, and treating for 10 hours at the reaction temperature of 900 ℃ to obtain an activated nickel smelting slag catalyst;
the activated nickel flash smelting slag of the embodiment is used for catalyzing the gasification of tar cracking of pine nut shells, the catalyst is placed in a fixed bed reactor, the tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:2, and the conversion rate of the tar is 78% when the catalytic cracking reaction temperature is 900 ℃.
Example 5: the catalyst of the present example is activated converter slag, wherein the converter slag comprises the following components: 50.70% of SiO2: 28.50%, CaO: 0.31%, MgO: 0.68%, Ni: 0.90%, Cu: 0.78%, the activation method is as follows:
(1) crushing the converter slag in a crusher, screening out particles with the granularity of 30 meshes, and drying at the temperature of 120 ℃ for 15 hours to remove moisture;
(2) calcining the dried converter slag for 15 hours at 850 ℃ in an oxygen-enriched atmosphere with the oxygen volume fraction of 60% to obtain an activated nickel smelting slag catalyst;
the activated converter slag of the embodiment is used for catalyzing the cracking of straw gasification tar, the catalyst is placed in a fixed bed reactor, the tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:1, and the conversion rate of the tar is 81% when the catalytic cracking reaction temperature is 900 ℃.
Example 6: the catalyst of the present example is activated converter slag, wherein the converter slag comprises the following components: 50.70% of SiO2：28.50%，CaO：0.31%，MgO：0.68%，Ni: 0.90%, Cu: 0.78%, the activation method is as follows:
(1) crushing the converter slag in a crusher, screening out particles with the granularity of 20 meshes, and drying at the temperature of 150 ℃ for 5 hours to remove moisture;
(2) loading the dried converter slag into a catalyst activation reactor, introducing mixed gas of carbon monoxide and argon, wherein the volume percentage of the carbon monoxide is 75%, and reducing for 8 hours at 950 ℃ to obtain an activated nickel smelting slag catalyst;
the catalyst of the embodiment is used for catalyzing the gasification and tar cracking of birch leftover materials, the catalyst is placed in a fixed bed reactor, tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:2, and the tar conversion rate is 77% when the catalytic cracking reaction temperature is 900 ℃.
Example 7: the catalyst of the embodiment is activated ore-smelting electric furnace slag, wherein the ingredients of the ore-smelting electric furnace slag are Fe: 25.20% of SiO2: 40.90%, CaO: 6.30%, MgO: 17.50%, Ni: 0.22%, Cu: 0.05%, the activation method is as follows:
(1) crushing the ore-smelting electric furnace slag in a crusher, screening out particles with the particle size of 40 meshes, and drying at the temperature of 130 ℃ for 15 hours to remove moisture;
(2) loading the dried ore thermoelectric furnace slag into a catalyst activation reactor, introducing combustible gas generated by lignite gasification into the reactor, wherein the main components of the combustible gas are hydrogen, carbon monoxide, methane, carbon dioxide, nitrogen and the like, and treating at the reaction temperature of 700 ℃ for 24 hours to obtain an activated nickel smelting slag catalyst;
the catalyst of the embodiment is used for catalyzing the pyrolysis of lignite gasification tar, the catalyst is placed in a fixed bed reactor, the tar enters the fixed bed reactor under the carrying of nitrogen, the mass ratio of the tar to the catalyst is 10:1, and the conversion rate of the tar is 72% when the catalytic pyrolysis reaction temperature is 850 ℃.
Claims (7)
1. The catalyst for catalyzing the gasification and tar cracking of the solid combustible material is characterized in that: the catalyst is generated in the nickel smelting process and the technological processThe nickel smelting slag comprises the following main chemical components: 25 to 42% of SiO2：30～45%，CaO：5～10%，MgO：5～10%，Ni：0.1～0.3%，Cu：0.1～0.2%。
2. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 1, wherein: the catalyst includes, but is not limited to, flash smelting slag, converter slag, ore-smelting electric furnace slag.
3. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 1, wherein: the catalyst is activated nickel smelting slag.
4. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 3, wherein the method for activating the nickel smelting slag comprises the following steps:
(1) crushing the nickel smelting slag, screening to obtain particles with the particle size of 20 ~ 40 meshes, and then drying for 5 ~ 24h at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and calcining the dried nickel smelting slag for 5 ~ 20 hours at the temperature of 750 ~ 1050 ℃ in the atmosphere of air, oxygen-enriched oxygen, pure oxygen or steam to obtain the activated nickel smelting slag.
5. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 3, wherein the method for activating the nickel smelting slag comprises the following steps:
(1) crushing the nickel smelting slag, screening to obtain particles with the particle size of 20 ~ 40 meshes, and then drying for 5 ~ 24h at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and (2) loading the dried nickel smelting slag into a catalyst activation reactor, introducing a mixture of reducing gas and inert gas, wherein the volume percentage of the reducing gas is 5 ~ 100% and reducing for 1 ~ 8h at 650 ~ 950 ℃ to obtain the activated nickel smelting slag.
6. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 5, wherein: reducing gases include, but are not limited to, hydrogen, carbon monoxide, methane, and inert gases include, but are not limited to, nitrogen, helium, argon.
7. The catalyst for catalyzing the cracking of solid combustible gasification tar according to claim 3, wherein the method for activating the nickel smelting slag comprises the following steps:
(1) crushing the nickel smelting slag, screening out particles with the particle size of 20 ~ 40 meshes, and then drying the particles for 5 ~ 24 hours at the temperature of 105 ~ 150 ℃ to remove moisture;
(2) and (3) putting the dry nickel smelting slag into a catalyst activation reactor, introducing combustible gas generated by gasification of solid combustible, and treating for 3 ~ 24h at the reaction temperature of 700-1000 ℃ to obtain the activated nickel smelting slag.
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