CN111841548A - Method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste - Google Patents
Method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste Download PDFInfo
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- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002910 solid waste Substances 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005188 flotation Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004058 oil shale Substances 0.000 claims description 5
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J35/61—Surface area
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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Abstract
A method for preparing a basic nickel silicate catalyst from silicon-containing industrial solid waste belongs to the technical field of resource utilization of solid waste. The invention adopts pretreated silicon-containing industrial solid waste as a silicon source, and the silicon-based precursor and the nickel-based precursor are added simultaneously to synthesize the three-dimensional basic nickel silicate by one-step hydrothermal synthesis, thereby overcoming the defect of complicated steps of a step-by-step synthesis method. According to the invention, silicon-containing industrial solid waste is used as a silicon source, and the nickel silicate material is prepared by a one-step hydrothermal method, so that the process is simple, the operation is simple and convenient, the preparation period is short, and a special reaction container is not needed; the used raw materials have low cost, high-value utilization of wastes is realized, and the method is suitable for batch production. The basic nickel silicate catalyst obtained by the invention has the advantages of high specific surface area, high mechanical strength, high activity, high stability, good thermal stability and low cost, and is suitable for high-temperature catalytic reaction after reduction.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, and particularly relates to a method for preparing a basic nickel silicate catalyst from silicon-containing industrial solid waste.
Background
Industrial solid waste is waste which is discharged in industrial and agricultural production and daily life and cannot be utilized temporarily or is discharged and is not utilized by the main body. The emission of industrial solid waste pollutes the environment while occupying land, and the full and reasonable utilization of the industrial solid waste has economic benefits, and more importantly, has great environmental protection and social benefits.
Nickel silicate has excellent physicochemical properties in battery materials, magnetic substances, catalyst carriers, and the like. At present, the research on the nano nickel-containing functional material mainly focuses on the one-dimensional fields of nano rods, nano wires, nano fibers and the like, and the research on the self-assembly of two-dimensional nano sheets into a three-dimensional structure is still few. Due to the characteristics of high specific surface, high stability and surface permeability of the material with the structure, and the staggered and stacked parts of the material can contain a large number of guest molecules or large-sized guests, the three-dimensional flower-shaped material has important progress in many technical fields such as catalysts, batteries, photoelectric materials, magnetic science and the like. The Ni/SiO can be obtained after the reduction of the basic nickel silicate2The sample, Ni, has 3d orbits and high activity and economy, and is widely used in various fields such as hydrogenation, alkylation, steam reforming, methanation and the like. In the catalytic process, the existence form of nickel and the structure of the catalyst have important influence on the catalytic effect. The three-dimensional flower-shaped basic nickel silicate/silicon dioxide catalyst has the characteristics of large specific surface area, strong catalytic activity and high catalyst carrying capacity.
The traditional preparation methods of nickel silicate and its compound are ammonia evaporation method and hydrothermal method, i.e. the interaction between silicon oxide-based material and soluble nickel salt occurs in the course of ammonia evaporation or hydrothermal process to form nickel silicate. The volatilization process of ammonia gas in the ammonia evaporation method can cause environmental pollution and material loss, and meanwhile, the relatively mild reaction condition and the relatively short action time can cause only part of silicon oxide to form nickel silicate, thereby reducing the quality of the nickel silicate. The hydrothermal self-assembly technology is an effective and practical technology in the current synthesis of multidimensional structures, is widely applied to the preparation of nano materials with different shapes, is relatively mature, and can obtain high-quality basic nickel silicate. However, in the preparation process of the silica-based material used in the above method, a commercial silica-based reagent such as methyl orthosilicate or ethyl orthosilicate is generally used as a silicon source, and a certain amount of expensive template such as P123, F127 or CTAB is added, so that the preparation conditions are harsh, the process is complex, and the cost is relatively high.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide the basic nickel silicate catalyst prepared from the silicon-containing industrial solid waste. The nickel silicate material prepared by the method can be used for high-temperature reactions such as methanation and the like after reduction.
The method for preparing the basic nickel silicate catalyst by using the silicon-containing industrial solid waste specifically comprises the following steps:
(1) crushing industrial solid waste containing silicon, placing the crushed industrial solid waste into a muffle furnace for roasting and activating at high temperature, and then mixing with NH4The solution F is 60-120%oReacting for 2-8 h under C, and filtering while the solution is hot so as to facilitate NH3Recovering;
(2) collecting NH generated in the reaction process of the step (1) by using deionized water3To obtain NH3·H2O；
(3) Adding the filtrate obtained in the step (1) into the NH in the step (2)3·H2In O, 50 to 80oC, heating and stirring for 1 h, and keeping the obtained slurry at 50-80 DEG CoC is settled for 3 hours and then filtered, and the obtained filter residue is washed and then is filtered by 50-90oC, vacuum drying for 12-36 hours to obtain a silicon dioxide sample, and recovering ammonium fluoride in the filtrate and returning to the step (1);
(4) then dispersing the dried silicon dioxide sample and water-soluble nickel salt in deionized water, carrying out ultrasonic treatment for 10 min, and then transferring the silicon dioxide sample and the water-soluble nickel salt to a hydrothermal kettle at a temperature of 150-240 DEG CoC, performing hydrothermal treatment for 12-48 h. Filtering, washing with anhydrous ethanol and distilled water for several times respectively at 40-80 deg.CoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
Specifically, in the step (1), the silicon-containing industrial solid waste is crushed and then placed in a muffle furnace in a range of 600-900%oAnd C, roasting for 2-6 h for activation.
Specifically, in the step (3), ammonium fluoride in the filtrate is subjected to vacuum concentration, crystallization and 60 percent crystallizationoAnd C, recovering and returning to the step (1) after vacuum drying and other treatment.
The silicon dioxide is a two-dimensional structure formed by connecting silicon-oxygen tetrahedrons through oxygen atoms, silicon hydroxyl with negative electricity on the surface can be neutralized by protons and alkali metal ions, and the silicon hydroxyl is stacked into blocks through electrostatic acting force. Under the reaction conditions, nickel ions react with silicon dioxide and self-assemble into three-dimensional flower-shaped basic nickel silicate, and the crystal form and Ni thereof3Si2O5(OH)4(JCPDS number 00-049-1859). The three-dimensional basic nickel silicate self-assembled by the nano-sheets is uniformly dispersed without agglomeration.
Further, the silicon-containing industrial solid waste comprises one or more of but not limited to iron tailings, antimony ore flotation tailings, silicon micropowder, yellow phosphorus slag, oil shale ash slag, waste diatomite and fluosilicic acid wastewater filter residue.
Further, the water-soluble nickel salt includes, but is not limited to, a mixture of one or more of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or hydrates thereof.
Further, the adding mass ratio of the water-soluble nickel salt to the silicon-containing industrial solid waste is 10: 1-30: 1.
Compared with the prior art, the invention has the following beneficial effects: the silicon-containing industrial solid waste is used as a silicon source, so that the cost is low, the template agent is not required to be removed, the complexity of the preparation method is simplified, and the cost is reduced; the density of the 'sheet-shaped objects' on the basic nickel silicate can be regulated and controlled by controlling the mass ratio of the nickel salt to the industrial solid waste, for example, in a certain range, the density of the 'sheet-shaped objects' on the basic nickel silicate is increased along with the increase of the content of the nickel salt, so that the specific surface area of the product and the loading capacity of the nickel can be regulated and controlled; the prepared basic nano nickel silicate has high purity and stable performance, is not easy to denature in air, and can still keep the original appearance after being roasted at high temperature. The advantages can save cost and facilitate large-scale preparation; the method has the advantages of simple and convenient operation, short preparation period, no pollution in the process, low cost of the used raw materials and suitability for batch production.
Drawings
FIG. 1 is an XRD pattern of a basic nickel silicate prepared in example 3 of the present invention;
FIG. 2 is an SEM photograph of basic nickel silicate prepared in example 3 of the present invention;
FIG. 3 is a TEM image of basic nickel silicate prepared in example 3 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
After being crushed, the fluosilicic acid wastewater filter residue is placed in a muffle furnace at 600 DEG CoRoasting for 6 hours for activation under C to obtain activated fluosilicic acid wastewater filter residue and 16 mol/L NH4The solution F is used as a reaction raw material and is at 100oHeating for 2 h under C, and filtering while the solution is hot. NH generated during the reaction3Collecting with deionized water to obtain NH3·H2And O. Adding the filtrate to the above NH3·H2O is middle, 50oHeating and stirring for 1 hr under C, stopping stirring, and adding the obtained slurry at 50 deg.CoC is settled for 3 h, then filtered and washed 80 timesoAnd C, vacuum drying for 12 h, and recycling ammonium fluoride in the filtrate as a reactant of the next reaction. Then dispersing the treated 1 g of solid powder in an aqueous solution containing 30g of nickel nitrate, carrying out ultrasonic treatment for 10 min, and then transferring the powder to a hydrothermal kettle at 240%oAnd C, performing hydrothermal treatment for 12 hours in an environment. Filtering, washing with anhydrous ethanol and distilled water respectively for several times at 60 deg.CoDrying in the oven for 24 h to obtain alkaliNickel silicate of the formula.
Example 2
Pulverizing oil shale ash and iron tailings, placing in a muffle furnace at 900 deg.CoRoasting for 2 h for activation under C, and adopting the activated oil shale ash slag, iron tailings and 22 mol/L NH4The solution F is used as a reaction raw material and is at 120 DEGoHeating for 8 h under C, and filtering while the solution is hot. NH generated during the reaction3Collecting with deionized water to obtain NH3·H2And O. Adding the filtrate to the above NH3·H2O in, 80oHeating and stirring for 1 hr under C, stopping stirring, and adding the obtained slurry at 80oC is settled for 3 h, then filtered and washed for 90 hoAnd C, vacuum drying for 36h, and recycling ammonium fluoride in the filtrate as a reactant of the next reaction. Then dispersing 1 g of treated oil shale ash and iron tailings in an aqueous solution containing 25 g of nickel nitrate, carrying out ultrasonic treatment for 10 min, and then moving the mixture into a hydrothermal kettle at 220 DEGoAnd C, performing hydrothermal treatment for 24 hours in an environment. Filtering, washing with anhydrous ethanol and distilled water respectively for several times at 60 deg.CoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
Example 3
Pulverizing waste diatomite, and placing in muffle furnace at 800 deg.CoRoasting for 6h for activation under C, adopting the activated waste diatomite and 10 mol/L NH4The solution F is used as a reaction raw material and is at 60 DEGoHeating for 6h under C, and filtering while the solution is hot. NH generated during the reaction3Collecting with deionized water to obtain NH3·H2And O. Adding the filtrate to the above NH3·H2O is middle, 50oHeating and stirring for 1 hr under C, stopping stirring, and adding the obtained slurry at 50 deg.CoC is settled for 3 h, then filtered and washed for 90 hoAnd C, vacuum drying for 26 h, and recycling ammonium fluoride in the filtrate as a reactant of the next reaction. Then dispersing 1 g of the treated waste diatomite in an aqueous solution containing 25 g of nickel nitrate, carrying out ultrasonic treatment for 10 min, and then transferring the waste diatomite to a hydrothermal kettle at 150 DEGoAnd C, performing hydrothermal treatment for 48 hours in the environment. Filtering, washing with anhydrous ethanol and distilled water respectively for several times at 70 deg.CoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
Example 4
Pulverizing silicon micropowder and yellow phosphorus slag, and placing in muffle furnace at 650oRoasting for 5 h for activation under C, and adopting the activated silicon micropowder, yellow phosphorus slag and 18 mol/L NH4The solution F is used as a reaction raw material and is at 60 DEGoHeating for 7 h under C, and filtering while the solution is hot. NH generated during the reaction3Collecting with deionized water to obtain NH3·H2And O. Adding the filtrate to the above NH3·H2In O, 60oHeating and stirring for 1 hr under C, stopping stirring, and adding the obtained slurry at 60 deg.CoC is settled for 3 h, then filtered and washed 60 hoAnd C, vacuum drying for 16 h, and recycling ammonium fluoride in the filtrate as a reactant of the next reaction. Then dispersing 1 g of the treated silicon micro powder and yellow phosphorus slag in an aqueous solution containing 15 g of nickel nitrate, carrying out ultrasonic treatment for 10 min, and then transferring the mixture into a hydrothermal kettle to carry out 180 minoAnd C, performing hydrothermal treatment for 36h in an environment. Filtering, washing with anhydrous ethanol and distilled water for several times respectively at 40 deg.CoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
Example 5
Crushing antimony ore flotation tailings, and placing the crushed antimony ore flotation tailings in a muffle furnace to 750oRoasting for 3 h and activating under C, and adopting the activated antimony ore flotation tailing powder and 12 mol/L NH4Solution F as the reaction material at 70oHeating for 5 h under C, and filtering while the solution is hot. NH generated during the reaction3Collecting with deionized water to obtain NH3·H2And O. Adding the filtrate to the above NH3·H2In O, 70oHeating and stirring for 1 hr under C, stopping stirring, and making the obtained slurry at 70 deg.CoC is settled for 3 h, then filtered and washed 50 hoAnd C, vacuum drying is carried out for 24 hours, and ammonium fluoride in the filtrate is recycled as a reactant of the next reaction. Then dispersing 1 g of the treated antimony ore flotation tailings in an aqueous solution containing 10 g of nickel nitrate, carrying out ultrasonic treatment for 10 min, and then moving the antimony ore flotation tailings to a hydrothermal kettle at 200 DEGoAnd C, performing hydrothermal treatment for 18 h in an environment. Filtering, washing with anhydrous ethanol and distilled water respectively for several times at 80 deg.CoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
Evaluation of catalyst Performance
Examples 1 to 5 were conductedTesting of catalytic Performance, selection of CO2The methanation reaction is a model reaction. Filling 100 mg of 20-40 mesh catalyst into a quartz reaction tube, reducing by hydrogen, and introducing reaction feed gas H2: CO2: N2(volume flow ratio 12: 3: 5). The reaction pressure is normal pressure, the mass space velocity is 60000 mL/h.g, and the reaction temperature is 450oC。
Table 1 shows CO in methanation reactions of the catalysts of examples 1 to 52Conversion and CH4Yield.
| Serial number | CO2Conversion (%) | CH4Selectivity (%) | CH4Yield (%) |
| Example 1 | 82 | 89 | 73 |
| Example 2 | 79 | 95 | 75 |
| Example 3 | 92 | 92 | 85 |
| Practice ofExample 4 | 85 | 88 | 75 |
| Example 5 | 87 | 93 | 81 |
As mentioned above, the basic nickel silicate catalyst prepared from the silicon-containing industrial solid waste has high activity and good application prospect in high-temperature reaction.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (6)
1. A method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste is characterized by comprising the following steps:
(1) crushing industrial solid waste containing silicon, placing the crushed industrial solid waste into a muffle furnace for roasting and activating at high temperature, and then mixing with NH4The solution F is 60-120%oReacting for 2-8 h under C, and filtering while the solution is hot so as to facilitate NH3Recovering;
(2) collecting NH generated in the reaction process of the step (1) by using deionized water3To obtain NH3·H2O；
(3) Adding the filtrate obtained in the step (1) into the NH in the step (2)3·H2In O, 50 to 80oC, heating and stirring for 1 h, and keeping the obtained slurry at 50-80 DEG CoC is settled for 3 hours and then filtered, and the obtained filter residue is washed and then is filtered by 50-90oVacuum drying under C12Obtaining a silicon dioxide sample, and recovering ammonium fluoride in the filtrate and returning to the step (1);
(4) then dispersing the dried silicon dioxide sample and water-soluble nickel salt in deionized water, carrying out ultrasonic treatment for 10 min, and then transferring the silicon dioxide sample and the water-soluble nickel salt to a hydrothermal kettle at a temperature of 150-240 DEG CoC, heating for 12-48 h, filtering, washing with absolute ethyl alcohol and distilled water for several times respectively at 40-80 DEGoAnd C, drying in an oven for 24 hours to obtain the basic nickel silicate.
2. The method for preparing the basic nickel silicate catalyst from the silicon-containing industrial solid waste according to claim 1, wherein in the step (1), the silicon-containing industrial solid waste is crushed and then placed in a muffle furnace to 600-900 degrees centigradeoAnd C, roasting for 2-6 h for activation.
3. The method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste according to claim 2, wherein in the step (3), ammonium fluoride in the filtrate is subjected to vacuum concentration, crystallization and 60 percent crystallizationoAnd C, recovering and returning to the step (1) after vacuum drying and other treatment.
4. The method for preparing the basic nickel silicate catalyst from the silicon-containing industrial solid waste according to claim 3, wherein the silicon-containing industrial solid waste is one or a mixture of more of iron tailings, antimony ore flotation tailings, silicon micropowder, yellow phosphorus slag, oil shale ash slag, waste diatomite and fluosilicic acid wastewater filter residues.
5. The method for preparing the basic nickel silicate catalyst from the silicon-containing industrial solid waste according to claim 3, wherein the water-soluble nickel salt is one or more of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or a mixture of hydrates thereof.
6. The method for preparing the basic nickel silicate catalyst from the silicon-containing industrial solid waste according to claim 5, wherein the adding mass ratio of the water-soluble nickel salt to the silicon-containing industrial solid waste is 10: 1-30: 1.
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