CN113042031A - Preparation method of low-temperature catalyst and prepared catalyst - Google Patents
Preparation method of low-temperature catalyst and prepared catalyst Download PDFInfo
- Publication number
- CN113042031A CN113042031A CN202110332830.4A CN202110332830A CN113042031A CN 113042031 A CN113042031 A CN 113042031A CN 202110332830 A CN202110332830 A CN 202110332830A CN 113042031 A CN113042031 A CN 113042031A
- Authority
- CN
- China
- Prior art keywords
- low
- temperature
- temperature catalyst
- tungsten ore
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 45
- 239000010937 tungsten Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 10
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 8
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229910052567 struvite Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 17
- -1 Bismuth (III) Iron Calcium carbonate Chemical compound 0.000 description 6
- 238000004846 x-ray emission Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RYFIDLXZHPNUFF-UHFFFAOYSA-N [Mo].O=[W](=O)=O Chemical compound [Mo].O=[W](=O)=O RYFIDLXZHPNUFF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- SYBFKRWZBUQDGU-UHFFFAOYSA-N copper manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Cu++] SYBFKRWZBUQDGU-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- LDMJFDJYOVHUMJ-UHFFFAOYSA-N stibanylidynesilicon Chemical compound [Sb]#[Si] LDMJFDJYOVHUMJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a low-temperature catalyst, relates to the technical field of catalysts, and is provided based on the problems of high production cost and difficult control of a production process of the conventional low-temperature denitration catalyst. The invention comprises the following steps: (1) an alkaline leaching process of tungsten ore; (2) a process for removing phosphorus and arsenic from crude sodium tungstate; (3) blending pure substances; (4) and (4) mixing, drying and calcining the mixture prepared in the step (3) in sequence to obtain a low-temperature catalyst finished product. The invention also provides a catalyst prepared by the preparation method. The invention achieves the purpose of primary purification by a tungsten ore reverse separation method, the tungsten ore is subjected to an alkali leaching link and a phosphorus and arsenic removal link to separate harmful and useless elements to obtain various elements beneficial to selective removal of NOx, and the tungsten ore reverse separation method is adopted, so that the tungsten ore purification process is shortened, and the production cost of the low-temperature catalyst is reduced.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a low-temperature catalyst and the prepared catalyst.
Background
Along with the development of national economy, population growth and the acceleration of urbanization process, the environmental pollution problem is increasingly highlighted, especially SO2And NOXThe problem of emissions. NO in the atmosphereXCan cause a series of problems of acid rain, photochemical smog, surface water eutrophication and the like which damage the environment and endanger the health of human beings. The most mature technology with the highest denitration efficiency at present is a Selective Catalytic Reduction (SCR) technology.
The traditional manufacturing process of the denitration catalyst needs to purchase a large amount of expensive chemical materials, for example, patent CN110841653A discloses a preparation method of a low-temperature denitration catalyst, which comprises the following steps: adding diatomite, coal-series kaolin, alumina powder, titanium dioxide powder and siderite into water, and then shaking at high temperature to obtain a mixture solution; filtering, drying and calcining the mixed solution to obtain a mixture; placing the obtained mixture in a container, adding deionized water, and adding Mn (NO)3)2、Ce(NO3)3·6H2O、Fe(NO3)3·9H2O and Sm (NO)3)3·6H2O, fully stirring and dissolving on a magnetic stirrer to obtain a mixed solution; slowly adding ammonium bicarbonate dropwise into the mixed solution to adjust the pH value to about 8-10, and adding NH dropwise3·H2O, adjusting the pH value of the solution to 9-10, continuously stirring, and aging at room temperature; and then placing the dried catalyst in an oven for drying, placing the dried catalyst in a muffle furnace for calcining, and then tabletting, crushing and sieving to obtain the low-temperature denitration catalyst. The problems with this technique are as follows: the purity requirement of chemical materials is high, so that the cost is high; the batch addition of various raw materials and the requirement of uniformity bring difficulty to the control of the mixing process.
Disclosure of Invention
The invention aims to solve the technical problems of high production cost and difficult control of a production process of the conventional low-temperature denitration catalyst.
The invention solves the technical problems through the following technical means:
a preparation method of a low-temperature catalyst comprises the following steps:
(1) the tungsten ore alkaline leaching process comprises the following steps: according to the proportion that the mass of the tungsten ore is 40-70% of that of the alkali compound, the tungsten ore is soaked in the alkali compound and leached for 2-5.5h at the temperature of 20-25 ℃; then, after the temperature is increased to 160-300 ℃, the leaching is continued for 10-20 min;
(2) the process for removing phosphorus and arsenic from crude sodium tungstate comprises the following steps: mixing the tungsten ore obtained after the alkaline leaching process in the step (1) with a salt solution at normal temperature, and stirring to obtain a mixture, wherein the mass of the salt solution is 5-50% of that of the tungsten ore obtained after the alkaline leaching process;
(3) pure substance preparation: adding a pure compound into the mixture prepared in the step (2) at normal temperature, and stirring and mixing uniformly;
(4) and (4) mixing, drying and calcining the mixture prepared in the step (3) in sequence to obtain a low-temperature catalyst finished product.
The invention achieves the purpose of primary purification by a tungsten ore reverse separation method, the tungsten ore is subjected to an alkali leaching link and a phosphorus and arsenic removal link to separate harmful and useless elements to obtain various elements beneficial to selective removal of NOx, and the tungsten ore reverse separation method is adopted, so that the tungsten ore purification process is shortened, and the production cost of the low-temperature catalyst is reduced.
Preferably, the tungsten ore in the step (1) comprises white tungsten concentrate or black tungsten concentrate.
Preferably, the alkali compound in step (1) comprises one or more of sodium carbonate, sodium hydroxide and sodium fluoride.
Preferably, the salt solution in step (2) comprises one or more of magnesium chloride, magnesium ammonium phosphate and magnesium ammonium phosphate hexahydrate.
Preferably, the pure compound in the step (3) is one or more of ammonium heptamolybdate, ammonium metatungstate, antimony acetate, niobium oxalate and the like.
Preferably, the mass of the pure compound in the step (3) is 0-10% of the mass of the mixture prepared in the step (2).
Preferably, the mixing temperature in the step (4) is 80-90 ℃, and the pH value is more than 8.
Preferably, the drying temperature in the step (4) is 40-60 ℃, and the drying period is 10-12 days.
Preferably, the calcination temperature in the step (4) is 600-615 ℃, and the calcination time is 30-32 h.
The invention also provides a low-temperature catalyst prepared by the preparation method.
The invention has the following beneficial effects: the invention achieves the purpose of primary purification by a tungsten ore reverse separation method, the tungsten ore is subjected to an alkali leaching link and a phosphorus and arsenic removal link to separate harmful and useless elements to obtain various elements beneficial to selective removal of NOx, and the tungsten ore reverse separation method is adopted, so that the tungsten ore purification process is shortened, and the production cost of the low-temperature catalyst is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a low-temperature catalyst comprises the following steps:
(1) leaching the scheelite concentrate for 2 hours at 20 ℃ by using a sodium carbonate solution, then raising the temperature to 160 ℃, and continuing to leach for 10 minutes, wherein the quality of the scheelite concentrate is 50% of that of the sodium carbonate solution;
(2) mixing tungsten ore obtained by the tungsten ore alkaline leaching process in the step (1) with magnesium ammonium phosphate hexahydrate solution at normal temperature, and stirring to obtain a mixture, wherein the mass of the magnesium ammonium phosphate hexahydrate solution is 20% of that of the tungsten ore obtained by the alkaline leaching process; the obtained mixture was subjected to elemental composition and content analysis, the results of which are shown in table 1;
(3) pure substance preparation: under the condition of normal temperature, adding ammonium heptamolybdate into the mixture prepared in the step (2), and stirring and mixing uniformly, wherein the mass of the added ammonium heptamolybdate is 10% of that of the mixture;
(4) and (3) sequentially carrying out mixing, drying and calcining treatment on the mixture prepared in the step (3), wherein the mixing temperature is 90 ℃, the pH value reaches more than 8, the drying period is 12 days, the drying temperature is 50 ℃, the calcining temperature is 615 ℃, and the calcining time is 32 hours, so as to obtain a low-temperature catalyst finished product.
Table 1 shows the results of analyzing the elemental composition and the content of the mixture of example 1
| Composition (I) | Tungsten trioxide | Molybdenum (Mo) | Manganese oxide | Copper (Cu) | Tin (Sn) | Silicon | Antimony (Sb) | Bismuth (III) | Iron | Calcium carbonate |
| Content/% | 65 | 0.7 | 0.04 | 0.15 | 0.13 | 0.2 | 0.02 | 0.1 | 0.1 | 5 |
The finished low temperature catalyst prepared in this example was subjected to X-ray fluorescence spectroscopy (XRF detection) and the results are shown in table 2.
Table 2 shows the results of X-ray fluorescence spectrum analysis of the finished low-temperature catalyst prepared in example 1
| Composition (I) | Vanadium pentoxide | Tungsten trioxide | Titanium dioxide | Molybdenum trioxide |
| Content/% | 2 | 5 | 84 | 4 |
The denitration efficiency of the finished low-temperature catalyst prepared in this example was measured, and the measurement results are shown in table 3.
Table 3 shows the results of the denitration efficiency measurements of the finished low-temperature catalyst prepared in example 1
| Temperature/. degree.C | 120 | 140 | 160 | 180 | 200 | 220 | 240 | 260 |
| Denitration efficiency/%) | 34.2 | 48.1 | 67.4 | 81.1 | 87.2 | 90.1 | 91.9 | 93.3 |
Example 2
A preparation method of a low-temperature catalyst comprises the following steps:
(1) leaching the black tungsten concentrate by using a sodium carbonate solution, leaching for 5 hours at 25 ℃, then raising the temperature to 200 ℃, and continuing to leach for 15 minutes, wherein the mass of the black tungsten concentrate is 50% of that of the sodium carbonate solution;
(2) mixing tungsten ore obtained after the tungsten ore is subjected to the alkali leaching process in the step (1) with magnesium ammonium phosphate hexahydrate, and stirring to obtain a mixture, wherein the mass of the magnesium ammonium phosphate hexahydrate solution is 20% of that of the tungsten ore obtained after the alkali leaching process; the obtained mixture was subjected to elemental composition and content analysis, the results of which are shown in table 4;
(3) pure substance preparation: under the condition of normal temperature, adding ammonium heptamolybdate into the mixture prepared in the step (2), and stirring and mixing uniformly, wherein the mass of the added ammonium heptamolybdate is 10% of that of the mixture;
(4) and (3) sequentially carrying out mixing, drying and calcining treatment on the mixture prepared in the step (3), wherein the mixing temperature is 90 ℃, the pH value reaches more than 8, the drying period is 12 days, the drying temperature is 50 ℃, the calcining temperature is 615 ℃, and the calcining time is 32 hours, so as to obtain a low-temperature catalyst finished product.
Table 4 shows the results of analyzing the elemental composition and the content of the mixture of example 1
| Composition (I) | Tungsten trioxide | Molybdenum (Mo) | Manganese oxide | Copper (Cu) | Tin (Sn) | Silicon | Antimony (Sb) | Bismuth (III) | Iron | Lead (II) |
| Content/% | 70 | 0.8 | 0.5 | 0.12 | 0.15 | 0.25 | 0.08 | 0.15 | 0.3 | 0.05 |
The finished low temperature catalyst prepared in this example was subjected to X-ray fluorescence spectroscopy (XRF detection) and the results are shown in table 5.
Table 5 shows the results of X-ray fluorescence spectrum analysis of the finished low-temperature catalyst prepared in example 2
| Composition (I) | Vanadium pentoxide | Tungsten trioxide | Titanium dioxide | Molybdenum trioxide |
| Content/% | 2 | 5 | 84 | 4 |
The denitration efficiency of the finished low-temperature catalyst prepared in this example was measured, and the measurement results are shown in table 6.
Table 6 shows the results of the denitration efficiency measurements of the finished low-temperature catalyst prepared in example 2
| Temperature/. degree.C | 120 | 140 | 160 | 180 | 200 | 220 | 240 | 260 |
| Denitration efficiency/%) | 35.2 | 47.1 | 69.6 | 83.2 | 88.5 | 92.5 | 94.9 | 96.6 |
Example 3
A preparation method of a low-temperature catalyst comprises the following steps:
(1) leaching the tungsten concentrate with a sodium carbonate solution for 5h at 2 ℃, then raising the temperature to 300 ℃, and continuing to leach for 20min, wherein the mass of the tungsten concentrate is 50% of that of the sodium carbonate solution;
(2) mixing tungsten ore obtained after the tungsten ore is subjected to the alkali leaching process in the step (1) with magnesium ammonium phosphate hexahydrate, and stirring to obtain a mixture, wherein the mass of the magnesium ammonium phosphate hexahydrate solution is 20% of that of the tungsten ore obtained after the alkali leaching process; the obtained mixture was subjected to elemental composition and content analysis, the results of which are shown in table 7;
(3) pure substance preparation: under the condition of normal temperature, adding ammonium heptamolybdate into the mixture prepared in the step (2), and stirring and mixing uniformly, wherein the mass of the added ammonium heptamolybdate is 10% of that of the mixture;
(4) and (4) sequentially carrying out mixing, drying and calcining treatment on the mixture prepared in the step (3), wherein the mixing temperature is 98 ℃, the pH value reaches 9, the drying period is 13 days, the drying temperature is 55 ℃, the calcining temperature is 610 ℃, and the calcining time is 31 hours, so as to obtain a low-temperature catalyst finished product.
Table 7 shows the results of analyzing the elemental composition and the content of the mixture of example 2
| Composition (I) | Tungsten trioxide | Molybdenum (Mo) | Manganese oxide | Copper (Cu) | Tin (Sn) | Silicon | Antimony (Sb) | Bismuth (III) | Iron | Lead (II) |
| Content/% | 68 | 0.9 | 0.6 | 0.22 | 0.25 | 0.2 | 0.09 | 0.17 | 0.2 | 0.04 |
The finished low temperature catalyst prepared in this example was subjected to X-ray fluorescence spectroscopy (XRF detection) and the results are shown in table 8.
Table 8 shows the results of X-ray fluorescence spectrum analysis of the finished low-temperature catalyst prepared in example 3
| Composition (I) | Vanadium pentoxide | Tungsten trioxide | Titanium dioxide | Molybdenum trioxide |
| Content/% | 2.5 | 8 | 82 | 5 |
The denitration efficiency of the finished low-temperature catalyst prepared in this example was measured, and the measurement results are shown in table 9.
Table 9 shows the results of measuring the denitration efficiency of the finished low-temperature catalyst prepared in example 3
| Temperature/. degree.C | 120 | 140 | 160 | 180 | 200 | 220 | 240 | 260 |
| Denitration efficiency/%) | 36.2 | 46.1 | 69.7 | 84.2 | 89.5 | 93.2 | 95.2 | 97.4 |
The invention achieves the purpose of primary purification by a tungsten ore reverse separation method, the tungsten ore is subjected to an alkali leaching link and a phosphorus and arsenic removal link to separate harmful and useless elements to obtain various elements beneficial to selective removal of NOx, and the tungsten ore reverse separation method is adopted, so that the tungsten ore purification process is shortened, and the production cost of the low-temperature catalyst is reduced.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a low-temperature catalyst is characterized by comprising the following steps:
(1) the tungsten ore alkaline leaching process comprises the following steps: soaking tungsten ore in alkali compound, and leaching at 20-25 deg.C for 2-5.5 hr; then, after the temperature is increased to 160-300 ℃, the leaching is continued for 10-20 min;
(2) the process for removing phosphorus and arsenic from crude sodium tungstate comprises the following steps: mixing the tungsten ore obtained by the tungsten ore alkaline leaching process treatment in the step (1) with a salt solution under the condition of normal temperature, and stirring to obtain a mixture;
(3) pure substance preparation: adding a pure compound into the mixture prepared in the step (2) at normal temperature, and stirring and mixing uniformly;
(4) and (4) mixing, drying and calcining the mixture prepared in the step (3) in sequence to obtain a low-temperature catalyst finished product.
2. The method for preparing a low-temperature catalyst according to claim 1, wherein: the tungsten ore in the step (1) comprises white tungsten concentrate or black tungsten concentrate.
3. The method for preparing a low-temperature catalyst according to claim 1, wherein: the alkali compound in the step (1) comprises one or more of sodium carbonate, sodium hydroxide and sodium fluoride.
4. The method for preparing a low-temperature catalyst according to claim 1, wherein: and (3) in the step (2), the salt solution comprises one or more of magnesium chloride, magnesium ammonium phosphate and magnesium ammonium phosphate hexahydrate.
5. The method for preparing a low-temperature catalyst according to claim 1, wherein: the pure compound in the step (3) is one or more of ammonium heptamolybdate, ammonium metatungstate, antimony acetate, niobium oxalate and the like.
6. The method for preparing a low-temperature catalyst according to claim 1, wherein: the mass of the pure compound in the step (3) is 0-10% of the mass of the mixture prepared in the step (2).
7. The method for preparing a low-temperature catalyst according to claim 1, wherein: the mixing temperature in the step (4) is 80-90 ℃, and the pH value is more than 8.
8. The method for preparing a low-temperature catalyst according to claim 1, wherein: in the step (4), the drying temperature is 40-60 ℃, and the drying period is 10-12 days.
9. The method for preparing a low-temperature catalyst according to claim 1, wherein: the calcination temperature in the step (4) is 600-615 ℃, and the calcination time is 30-32 h.
10. A low-temperature catalyst obtained by the method for preparing a low-temperature catalyst according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110332830.4A CN113042031A (en) | 2021-03-29 | 2021-03-29 | Preparation method of low-temperature catalyst and prepared catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110332830.4A CN113042031A (en) | 2021-03-29 | 2021-03-29 | Preparation method of low-temperature catalyst and prepared catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113042031A true CN113042031A (en) | 2021-06-29 |
Family
ID=76516364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110332830.4A Pending CN113042031A (en) | 2021-03-29 | 2021-03-29 | Preparation method of low-temperature catalyst and prepared catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113042031A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072927A (en) * | 2022-08-01 | 2022-09-20 | 中南大学 | Method for recovering tungsten from tungsten smelting wastewater |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006167526A (en) * | 2004-12-14 | 2006-06-29 | Babcock Hitachi Kk | Chemical for regenerating denitration catalyst and regeneration method using the same |
| JP2009006226A (en) * | 2007-06-27 | 2009-01-15 | Babcock Hitachi Kk | Method for regenerating catalyst |
| CN102962055A (en) * | 2012-11-22 | 2013-03-13 | 中节能六合天融环保科技有限公司 | Molybdenum-based low-temperature denitration catalyst and preparation thereof |
| CN106732531A (en) * | 2016-12-09 | 2017-05-31 | 大唐国际化工技术研究院有限公司 | A kind of SCR denitration and its production and use |
| CN108014780A (en) * | 2016-10-31 | 2018-05-11 | 龙岩紫荆创新研究院 | A kind of preparation method of denitration catalyst carrier and the carrier and the denitrating catalyst of application carrier preparation |
| CN108246283A (en) * | 2018-02-13 | 2018-07-06 | 宜兴市宜刚环保工程材料有限公司 | A kind of denitrating catalyst and preparation method thereof |
| CN110240200A (en) * | 2019-06-28 | 2019-09-17 | 中南大学 | The method of tungsten is extracted from tungsten ore |
| CN110508273A (en) * | 2019-07-26 | 2019-11-29 | 华侨大学 | A kind of low temperature vanadium titanium-based SCR denitration and preparation method thereof |
| CN112495369A (en) * | 2020-11-22 | 2021-03-16 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium-tungsten titanium-based SCR denitration catalyst and preparation method thereof |
-
2021
- 2021-03-29 CN CN202110332830.4A patent/CN113042031A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006167526A (en) * | 2004-12-14 | 2006-06-29 | Babcock Hitachi Kk | Chemical for regenerating denitration catalyst and regeneration method using the same |
| JP2009006226A (en) * | 2007-06-27 | 2009-01-15 | Babcock Hitachi Kk | Method for regenerating catalyst |
| CN102962055A (en) * | 2012-11-22 | 2013-03-13 | 中节能六合天融环保科技有限公司 | Molybdenum-based low-temperature denitration catalyst and preparation thereof |
| CN108014780A (en) * | 2016-10-31 | 2018-05-11 | 龙岩紫荆创新研究院 | A kind of preparation method of denitration catalyst carrier and the carrier and the denitrating catalyst of application carrier preparation |
| CN106732531A (en) * | 2016-12-09 | 2017-05-31 | 大唐国际化工技术研究院有限公司 | A kind of SCR denitration and its production and use |
| CN108246283A (en) * | 2018-02-13 | 2018-07-06 | 宜兴市宜刚环保工程材料有限公司 | A kind of denitrating catalyst and preparation method thereof |
| CN110240200A (en) * | 2019-06-28 | 2019-09-17 | 中南大学 | The method of tungsten is extracted from tungsten ore |
| CN110508273A (en) * | 2019-07-26 | 2019-11-29 | 华侨大学 | A kind of low temperature vanadium titanium-based SCR denitration and preparation method thereof |
| CN112495369A (en) * | 2020-11-22 | 2021-03-16 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium-tungsten titanium-based SCR denitration catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄尔君编著: "《化学选矿》", 31 May 1990 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072927A (en) * | 2022-08-01 | 2022-09-20 | 中南大学 | Method for recovering tungsten from tungsten smelting wastewater |
| CN115072927B (en) * | 2022-08-01 | 2023-06-09 | 中南大学 | Method for recycling tungsten from tungsten smelting wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927170B (en) | Preparation method and application of low-temperature flue gas denitration catalyst based on CoMnAl hydrotalcite-like compound | |
| CN108927169A (en) | A kind of preparation method and application of hydrotalcite CoMnFe metal composite oxide denitrating catalyst | |
| CN111135860A (en) | Rare earth metal modified Cu-SSZ-13 molecular sieve and preparation method and application thereof | |
| CN1917955A (en) | Exhaust gas catalyst | |
| CN104014331A (en) | Preparation method of mesoporous titanium dioxide ball supported Mn-Ce-W compound oxide denitration catalyst | |
| CN105478133A (en) | Low-cost SCR denitration catalyst and preparation method thereof | |
| CN113198525B (en) | Catalyst for synergistic purification of laughing gas decomposition and NOx catalytic reduction under low-temperature condition and preparation method thereof | |
| DE102010010588A1 (en) | Process for the regeneration of a catalyst for the production of methacrylic acid and process for the preparation of methacrylic acid | |
| CN108435189A (en) | A kind of samarium doping iron-based denitrating catalyst and preparation method thereof with water resistant sulfur resistance | |
| CN109012687B (en) | MnO (MnO)2Preparation method and application of/CoAl-LDO (low-temperature flue gas denitration catalyst) | |
| CN113042031A (en) | Preparation method of low-temperature catalyst and prepared catalyst | |
| CN110947416B (en) | For NH 3 Iron/molecular sieve catalyst of SCR (selective catalytic reduction), and preparation method and application thereof | |
| CN100457267C (en) | Process of making mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins | |
| CN113070097A (en) | NO for ammonia selective catalytic reductionxCopper-based catalyst and preparation method thereof | |
| CN108128784A (en) | The preparation method of Cu-Ce-La-SSZ-13 molecular sieve catalysts | |
| CN111437875B (en) | Cerium-iron molecular sieve based catalyst with wide temperature range and preparation method thereof | |
| CN108236943A (en) | A kind of preparation method of vanadium oxide catalyst | |
| CN113198445B (en) | Red mud SCR catalyst and preparation method and application thereof | |
| CN1043296A (en) | Titanyl compound with stability property | |
| CN110694640B (en) | Water-resistant sulfur-resistant denitration catalyst and preparation method thereof | |
| CN109847745A (en) | A kind of preparation method of ruthenium system ultralow temperature denitrating catalyst | |
| CN112495367A (en) | Oxygen-enriched MoTiOxCatalyst, preparation method and application thereof | |
| CN112844467A (en) | Denitration catalyst and preparation method and application thereof | |
| CN113019353A (en) | Anti-poisoning ion exchange type attapulgite-based denitration catalyst, and preparation method and application thereof | |
| CN115138371B (en) | Selective catalytic oxidation catalyst for reducing sulfur pollutants, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |