CN110711584A - Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof - Google Patents
Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000000629 steam reforming Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000571 coke Substances 0.000 title claims description 27
- 239000003245 coal Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 238000002309 gasification Methods 0.000 claims abstract description 7
- 238000002407 reforming Methods 0.000 claims abstract description 7
- 239000012684 catalyst carrier precursor Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 25
- 150000002815 nickel Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 8
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 20
- 239000011269 tar Substances 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000011285 coke tar Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 description 21
- 238000005406 washing Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000003077 lignite Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- LRHSENVDAQAWKP-UHFFFAOYSA-N [C].CC1=CC=CC=C1 Chemical compound [C].CC1=CC=CC=C1 LRHSENVDAQAWKP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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Abstract
The invention discloses a semicoke-loaded coke tar steam reforming catalyst and a preparation method and application thereof. The invention takes low-cost low-rank coal as a catalyst carrier precursor, enriches the surface acid sites of the catalyst, strengthens the interaction of the carrier and metal, improves the atom utilization efficiency and further improves the activity of the catalyst. Greatly reduces the production cost, can be used for catalyzing the reforming of biomass or low-rank coal gasification tar steam, and has higher carbon conversion rate.
Description
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to a semicoke-loaded coke oil steam reforming catalyst and a preparation and application method thereof.
Background
Gasification is one of the main technologies for clean and efficient conversion of coal, is widely applied to the fields of chemical synthesis, industrial gas, metallurgical reducing gas production, coal-based poly-generation and the like, and is the core and key of the technology.
The tar is an inevitable byproduct of low-temperature gasification of low-rank coal, and the content of the tar in the discharged gasification gas is 5-75 g/Nm3The tar is not uniformly pyrolyzed and can block pipelines and corrode downstream equipment, so that the catalyst in the subsequent process is inactivated, and a plurality of obstacles are caused to the clean utilization of low-rank coal.
In various tar removal technologies, catalytic reforming not only has high tar removal efficiency and relatively mild operating conditions, but also can fully utilize a large amount of water vapor and CO in the raw synthesis gas2Reforming tar to H2And CO, and the like, and catalytic reforming of tar is considered to be the most promising tar removal method for large-scale application.
Different types of catalysts are used for the removal of tar from gasification gas, such as high temperature roasted rock, molecular sieves, iron ore, Alkali and Alkaline Earth Metals (AAEMs), nickel based catalysts, and noble metal catalysts, wherein nickel based catalysts possess optimal catalytic activity. The nickel-based catalyst is generally supported on a metal oxide support, a molecular sieve support, a natural ore support, and a coke support. Compared with other carriers, the coal coke or biomass coke serving as a pyrolysis byproduct is cheap and easy to obtain, contains abundant alkali metals and alkaline earth metals, has high specific surface area and oxygen-containing functional groups, and has certain tar removal activity.
Wang et al (Applied Energy,2011,88(5): 1656-.
CN 107715884A discloses a metal-loaded biomass semi-coke catalyst and a preparation method thereof, wherein a metal active component is loaded on a biomass precursor subjected to acid washing pretreatment through isovolumetric impregnation, the metal active component comprises a second active metal formed by active metal Ni and one of Fe, Co or Cu, and the tar reforming catalyst is prepared through sequential temperature rise. The method adopts equal-volume impregnation to load the active component, the active component is difficult to be uniformly dispersed in a pore structure of the carrier, the interaction force between the carrier and the metal is weak, and the utilization rate of the metal active component is low in the catalytic process.
CN 103846088A discloses a preparation and application method of a nickel-based biomass tar steam reforming catalyst, the catalyst takes lignite pretreated by sodium hydroxide as a carrier precursor, the lignite is subjected to ion operation and then is subjected to standing filtration, and the volatile components of the lignite are removed through temperature programming, so that the nickel-based biomass tar steam reforming catalyst is obtained. After lignite is treated by sodium hydroxide, acid sites (oxygen-containing functional groups) on the surface of a carrier are damaged, and the interaction of metal and the carrier is greatly weakened; secondly, after ion exchange, without a water washing step, the excessive nickel salt adheres to the surface of the carrier, so that the catalyst has a low specific surface area and a less porous structure.
Disclosure of Invention
The invention aims to disclose a semicoke-supported coke oil steam reforming catalyst, a preparation method and application thereof, so as to overcome the defects in the prior art and meet the application requirements of the related fields.
The semicoke-based supported tar steam reforming catalyst takes low-rank coal pretreated by an oxidant as a catalyst carrier precursor and Ni as a metal active component. Wherein the mass percent of Ni is 7-13%, preferably 7.2-12.1%;
the preparation method of the semicoke-based supported tar steam reforming catalyst comprises the following steps:
(1) mixing an oxidant aqueous solution with target coal, stirring for 2-6 h, preferably 4h at 30-50 ℃, preferably 40 ℃, and then collecting low-rank coal oxidized by an oxidant from a system;
the ratio of the target coal to the oxidant is 5-10 mL/g, preferably 5 mL/g;
the oxidant is selected from nitric acid or hydrogen peroxide, and the mass concentration of the oxidant aqueous solution is 10-30%;
the target coal is low-rank coal particles with the particle size of 80-160 meshes, and the industrial analysis and the elemental analysis of the target coal sample are shown in table 1;
TABLE 1 Industrial and elemental analysis of target coal samples
The method for collecting the oxidized low-rank coal comprises the steps of filtering, washing with water to be neutral, and drying at the temperature of 60-80 ℃ until the moisture content is lower than 5% by mass;
(2) mixing the product obtained in the step (1) with a nickel salt aqueous solution with the pH value of 10-12, stirring at 25-35 ℃ for 16-32 hours, preferably 24 hours, and then collecting a catalyst precursor from the system;
the collection method comprises the following steps:
filtering the obtained mixture, collecting filter residues, washing the filter residues with water to be neutral, and drying the filter residues at the temperature of 60-80 ℃, preferably 70 ℃ until the water content is lower than 5% by mass;
the concentration of the nickel salt aqueous solution is 0.1-0.3 mol/L, preferably 0.2 mol/L;
the nickel salt is selected from more than one of nickel acetate tetrahydrate, nickel nitrate hexahydrate, nickel sulfate hexahydrate or anhydrous nickel chloride, and preferably nickel acetate tetrahydrate;
the preparation method of the nickel salt aqueous solution is conventional, wherein the pH can be adjusted by alkaline substances, such as ammonia water, sodium hydroxide solution or potassium hydroxide solution, and ammonia water is preferred;
the mixing ratio of the nickel salt solution to the low-rank coal oxide is 5-15 mL/g, and preferably 10 mL/g.
(3) Pyrolyzing the catalyst precursor in the step (2) in an inert atmosphere to stabilize the crystal form of elemental nickel on the surface of the catalyst, removing volatile components in a carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-loaded coke oil-steam reforming catalyst;
the pyrolysis comprises the following steps:
heating the mixture from room temperature to 550-700 ℃, preferably 600 ℃;
the heating rate is 5-10 ℃/min, preferably 10 ℃/min;
the retention time is 1-3 hours, preferably 2 hours;
the semicoke-loaded coke tar steam reforming catalyst can be used for catalyzing the steam reforming of biomass or low-rank coal gasification coke tar.
According to the invention, cheap low-rank coal is used as a catalyst carrier precursor, and in the active component loading process, the characteristic that the low-rank coal contains rich oxygen-containing functional groups is fully considered, so that the low-rank coal is subjected to oxidation treatment in different degrees, the number of the oxygen-containing functional groups in the coal is adjusted, and the nickel loading capacity is improved while good dispersion degree and crystallite size are maintained. In addition, the number of oxygen-containing functional groups on the surface of the carrier is increased through oxidation treatment, so that the surface acid sites of the catalyst are enriched, the interaction of the carrier and metal is enhanced, the atom utilization efficiency is improved, and the activity of the catalyst is further improved.
The invention has the beneficial effects that:
the raw material of the carrier of the catalyst is low-rank coal, the number of oxygen-containing functional groups on the surface of the coal is increased by oxidation pretreatment, and the low-rank coal is Ni2+The effective load on the coal sample provides more exchange sites, so that the catalyst maintains good Ni dispersion degree and smaller crystallite size in the process of increasing the Ni load;
the invention enhances the carrier-metal interaction of the catalyst while improving the loading capacity of the catalyst, the catalyst is easy to form more defect structures with negative electrons in the catalytic tar steam reforming process, the combination probability of the catalyst and activated tar fragments is increased, and the atomic utilization efficiency of the catalyst is further improved;
in the ion exchange process, ammonia water is used to regulate the pH of metal salt solution, so that nickel salt is mainly Ni (NH)4)6 2+On the other hand, the O-H bond in the oxygen-containing functional group on the surface of the coal is easier to break, and Ni (NH) is promoted4)6 2+Bonding with oxygen-containing functional groups on the surface of the coal;
the carrier of the catalyst is low-rank coal, the specific surface area of the catalyst is increased through oxidation pretreatment, and redundant nickel salt is washed away through a water washing step after the ion exchange step is finished, so that the dispersion degree of Ni is improved;
the semicoke loaded coke oil steam reforming catalyst carrier selects low-rank coal, and the loaded nickel salt is reduced in situ in the coal sample pyrolysis devolatilization process to obtain a reduced Ni component, so that the hydrogen reduction step is omitted, and the semicoke loaded coke oil steam reforming catalyst carrier is simple and convenient to use;
coal is used as one ore resource, contains abundant alkali metal and alkaline earth metal, and can be used as a catalyst auxiliary agent to play a catalytic role in the tar steam reforming process, so that the catalytic performance of the catalyst is improved to a certain extent, and compared with other types of tar reforming catalysts, the coal tar reforming catalyst omits an auxiliary agent adding step, so that the production cost is greatly reduced;
drawings
FIG. 1 is a TEM image of a semicoke-supported coke steam reforming catalyst prepared in example 3 of the present invention;
FIG. 2 is a TEM image of a semicoke-supported coke steam reforming catalyst prepared in example 5 of the present invention;
FIG. 3 is an XRD pattern of a semicoke-supported coke vapor reforming catalyst prepared according to various embodiments of the present invention;
Detailed Description
The semicoke-supported coke oil steam reforming catalyst can be evaluated by the following method:
the catalyst is placed in a fixed bed reactor, nitrogen is used as carrier gas, toluene and water vapor are vaporized by a preheating furnace and then are sent into the reactor, and the space velocity of reactants in the reactor is 7200h-1The reaction temperature is 600 ℃, and CO and H are obtained2And (4) waiting for small molecule gas products.
Collecting the product gas, detecting the gas composition by Raman gas analyzer (RLGA) to obtain nCO、
By controlling the flow rate of toluene entering the reactor and the reaction time, the method is obtained
The carbon conversion was then calculated and the toluene carbon conversion was defined as formula (1):
wherein:
nCOrepresents the amount of CO species in the product;
in the examples, the amounts of the substances are by mass unless otherwise specified.
Example 1
100mL of aqueous hydrogen peroxide solution with the mass fraction of 10% is prepared.
Preparation of oxidized low-rank coal:
soaking 20g of low-rank coal into a hydrogen peroxide solution with the mass fraction of 10%, uniformly mixing, stirring for 4h at 40 ℃, filtering, washing filter residues to be neutral, and drying at 70 ℃ until the water content is 5%; obtaining oxidized low-rank coal;
preparing a metal salt solution: weighing 5g of nickel acetate tetrahydrate, and dissolving in 100mL of deionized water; adding ammonia water with the mass concentration of 25%, and adjusting the pH value of the salt solution to 11;
ion exchange: adding 10g of the low-rank oxidized coal into the prepared nickel salt solution, stirring for 24 hours at 30 ℃, filtering, washing filter residues to be neutral, and drying at 70 ℃ until the water content is 3%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 600 ℃ from room temperature;
the heating rate is 10 ℃/min;
the retention time is 2 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 7.9%.
nCO＝0.29mol；
Carbon conversion was calculated according to formula (1): the carbon conversion was 72.2%.
Example 2
100mL of 20% aqueous hydrogen peroxide solution was prepared.
Preparation of oxidized low-rank coal:
soaking 20g of low-rank coal into the hydrogen peroxide solution with the mass fraction of 20%, uniformly mixing, stirring for 6h at 30 ℃, filtering, washing filter residues to be neutral, and drying at 80 ℃ until the water content is 3%; obtaining oxidized low-rank coal;
preparing a metal salt solution:
weighing 3.9g of anhydrous nickel chloride, and dissolving in 100mL of deionized water; adding ammonia water with the mass concentration of 25%, and adjusting the pH value of the salt solution to 10;
ion exchange: adding 20g of the low-rank oxidized coal into the prepared nickel salt solution, stirring for 32 hours at 25 ℃, filtering, washing filter residues to be neutral, and drying at 80 ℃ until the water content is 3%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 550 ℃ from room temperature;
the heating rate is 5 ℃/min;
the retention time is 3 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 8.5%.
nCO＝0.33mol；
Carbon conversion was calculated according to formula (1): the carbon conversion was 74.7%.
Example 3
100mL of aqueous solution of hydrogen peroxide with the mass fraction of 30% is prepared.
Preparation of oxidized low-rank coal:
soaking 10g of low-rank coal into the hydrogen peroxide solution with the mass fraction of 30%, uniformly mixing, stirring for 2h at 50 ℃, filtering, washing filter residues to be neutral, and drying at 60 ℃ until the water content is 4% to obtain oxidized low-rank coal;
preparing a metal salt solution: weighing 2.7g of nickel nitrate hexahydrate, and dissolving in 100mL of deionized water; adding a sodium hydroxide solution with the mass concentration of 40%, and adjusting the pH value of the salt solution to 12;
ion exchange: adding 7g of the low-rank oxidized coal into the prepared nickel salt solution, stirring for 16h at 35 ℃, filtering, washing filter residues to be neutral, and drying at 60 ℃ until the water content is 4%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 700 ℃ from room temperature;
the heating rate is 8 ℃/min;
the retention time is 1 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 9.9%.
nCO＝0.35mol；
Carbon conversion was calculated according to formula (1): the carbon conversion rate was 76.7%;
as can be seen from the TEM spectrum of fig. 1, the metal nanoparticles are uniformly embedded in the coke matrix, showing good nickel dispersion with an average nickel particle size of only 4.3 nm.
Example 4
100mL of 20% nitric acid aqueous solution is prepared.
Preparation of oxidized low-rank coal:
soaking 15g of low-rank coal into the nitric acid aqueous solution with the mass fraction of 20%, uniformly mixing, stirring for 4 hours at 40 ℃, filtering, washing filter residues to be neutral, and drying at 70 ℃ until the water content is 5%; obtaining oxidized low-rank coal;
preparing a metal salt solution: weighing 5.3g of nickel sulfate hexahydrate, and dissolving in 100mL of deionized water; adding 30% by mass potassium hydroxide solution, and adjusting the pH value of the salt solution to 11;
ion exchange: adding 10g of the low-rank oxidized coal into the prepared nickel salt solution, stirring for 26h at 30 ℃, filtering, washing filter residues to be neutral, and drying at 80 ℃ until the water content is 5%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 650 ℃ from room temperature;
the heating rate is 10 ℃/min;
the retention time is 2 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 10.8%.
nCO＝0.27mol；
Carbon conversion was calculated according to formula (1): the carbon conversion rate was 66.9%;
example 5
100mL of nitric acid aqueous solution with the mass fraction of 30% is prepared.
Preparation of oxidized low-rank coal:
soaking 20g of low-rank coal into a nitric acid aqueous solution with the mass fraction of 30%, uniformly mixing, stirring for 5 hours at 50 ℃, filtering, washing filter residues to be neutral, and drying at 80 ℃ until the water content is 1%; obtaining oxidized low-rank coal;
preparing a metal salt solution: weighing 2.5g of nickel acetate tetrahydrate, and dissolving in 100mL of deionized water; adding ammonia water with the mass concentration of 25%, and adjusting the pH value of the salt solution to 10;
ion exchange: adding 5g of the low-rank oxidized coal into the prepared nickel salt solution, stirring for 24 hours at 30 ℃, filtering, washing filter residues to be neutral, and drying at 70 ℃ until the water content is 4%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps: heating to 600 ℃ from room temperature;
the heating rate is 10 ℃/min;
the retention time is 2 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 12.1%.
nCO＝0.26mol；
Carbon conversion was calculated according to formula (1): the carbon conversion rate was 67%;
as can be seen from the TEM spectrum of fig. 2, the metal nanoparticles are embedded in the coke matrix and show better nickel dispersion with an average nickel particle size of 6.4 nm.
As shown in fig. 3, the metal crystal form of the catalyst prepared in each example was characterized by XRD, and each catalyst maintained a stable elemental crystal form of nickel.
The average crystallite size of Ni of the catalyst of each example is obtained by calculating Ni (111) crystal face through a Debye-Sheer formula, and the specific surface area of part of the catalyst is measured by a nitrogen adsorption method. The measurement results are shown in Table 2.
Table 2 characterization results of catalyst physical properties
Comparative example 1
Preparing a metal salt solution: weighing 5g of nickel acetate tetrahydrate, and dissolving in 100mL of deionized water; adding ammonia water with the mass concentration of 25%, and adjusting the pH value of the salt solution to 11;
ion exchange: adding 10g of raw coal carrier into the prepared nickel salt solution, stirring for 24h at 30 ℃, filtering, washing filter residue to be neutral, and drying at 70 ℃ until the water content is 5%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 600 ℃ from room temperature;
the heating rate is 10 ℃/min;
the retention time is 2 h;
and analyzing the Ni loading amount of the catalyst by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and obtaining the mass fraction of Ni in the catalyst to be 5.7%.
nCO＝0.05mol；
Carbon conversion was calculated according to formula (1): the carbon conversion was 22%.
Comparative example 2
Preparing a metal salt solution: 4.3g of nickel acetate tetrahydrate are prepared into 10mL of aqueous solution.
Dipping: adding 10g of raw coal carrier into the prepared nickel salt solution, stirring for 8h at 30 ℃, and drying at 70 ℃ until the water content is 3%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 600 ℃ from room temperature;
the heating rate is 10 ℃/min;
the retention time is 2 h;
the mass fraction of Ni in the catalyst is 10%.
nCO＝0.005mol；
Carbon conversion was calculated according to formula (1): the carbon conversion rate is 4.6%;
comparative example 3
Preparing a metal salt solution: 5.0g of nickel acetate tetrahydrate is prepared into 40mL of aqueous solution.
Pressure impregnation: adding 10g of raw coal carrier into the prepared nickel salt solution, uniformly mixing, placing in a pressure kettle, sealing, keeping at 140 ℃ for 5h, standing the obtained mixture for 1h, filtering at 70 ℃, and drying until the water content is 4%;
and (3) catalyst molding: pyrolyzing the dried filter residue in an inert atmosphere to stabilize the crystal form of the elemental nickel on the surface of the catalyst, removing volatile components in the carrier, increasing the specific surface area of the catalyst, and pyrolyzing to obtain the semicoke-supported coke oil steam reforming catalyst;
the pyrolysis comprises the following steps:
heating to 600 ℃ from room temperature;
the heating rate is 10 ℃/min; the retention time is 2 h;
nCO＝0.003mol；
carbon conversion was calculated according to formula (1): the carbon conversion was 4.9%.
Claims (10)
1. The semicoke-loaded coke oil-steam reforming catalyst is characterized in that low-rank coal pretreated by an oxidant is used as a catalyst carrier precursor, and Ni is used as a metal active component.
2. The semicoke-supported coke steam reforming catalyst according to claim 1, wherein the mass percentage of Ni is 7 to 13%.
3. The semicoke-supported coke steam reforming catalyst according to claim 2, wherein the mass percentage of Ni is 7.2 to 12.1%.
4. The preparation method of the semicoke-based supported tar steam reforming catalyst is characterized by comprising the following steps of:
(1) mixing and stirring an oxidant aqueous solution and target coal, and then collecting low-rank coal oxidized by an oxidant from a system;
(2) mixing and stirring the product obtained in the step (1) and a nickel salt aqueous solution with the pH value of 10-12, and then collecting a catalyst precursor from a system;
(3) and (3) pyrolyzing the catalyst precursor in the step (2) in an inert atmosphere to obtain the semicoke-loaded coke-oven water vapor reforming catalyst.
5. The method according to claim 4, characterized in that in the step (1), the mixture is stirred for 2-6 hours at 30-50 ℃, and then the low-rank coal oxidized by the oxidant is collected from the system, wherein the ratio of the target coal to the oxidant is 5-10 mL/g; the oxidant is selected from nitric acid or hydrogen peroxide.
6. The method according to claim 4, wherein in the step (2), the product obtained in the step (1) is mixed with a nickel salt aqueous solution with the pH value of 10-12, the mixture is stirred for 16-32 hours at the temperature of 25-35 ℃, and then a catalyst precursor is collected from the system;
the pH value of the nickel salt aqueous solution is adjusted by ammonia water;
the mixing ratio of the nickel salt solution to the low-rank coal oxide is 5-15 mL/g.
7. The method of claim 6, wherein the nickel salt is selected from one or more of nickel acetate tetrahydrate, nickel nitrate hexahydrate, nickel sulfate hexahydrate, and anhydrous nickel chloride.
8. The method according to claim 6, wherein the concentration of the nickel salt aqueous solution is 0.1 to 0.3 mol/L.
9. The method of claim 4, wherein in step (3), said pyrolyzing comprises the steps of: heating from room temperature to 550-700 ℃, wherein the heating rate is 5-10 ℃/min, and the retention time is 1-3 hours.
10. The application of the semicoke-supported tar steam reforming catalyst according to any one of claims 1 to 3, wherein the catalyst is used for catalyzing biomass or low-rank coal gasification tar steam reforming.
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