CN113351197A - Preparation method of SCR denitration catalyst - Google Patents
Preparation method of SCR denitration catalyst Download PDFInfo
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- CN113351197A CN113351197A CN202010142598.3A CN202010142598A CN113351197A CN 113351197 A CN113351197 A CN 113351197A CN 202010142598 A CN202010142598 A CN 202010142598A CN 113351197 A CN113351197 A CN 113351197A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 59
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 39
- 239000002244 precipitate Substances 0.000 claims abstract description 34
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 26
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 25
- -1 sulfuric acid rare earth Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 description 17
- 229910044991 metal oxide Inorganic materials 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses a preparation method of an SCR denitration catalyst, which comprises the following steps: 1) dissolving the rare earth oxalic acid wastewater treatment neutralization slag by using sulfuric acid, wherein calcium-based components in the rare earth oxalic acid wastewater treatment neutralization slag form precipitates in a calcium sulfate form, and converting rare earth into sulfuric acid rare earth to enter a solution; after the precipitation conversion is finished, adding concentrated sulfuric acid to ensure that the mass concentration of sulfuric acid in the solution is 2.5-10%, and then separating calcium sulfate precipitation from a sulfuric acid rare earth solution while the solution is hot; 2) adding a saturated oxalic acid solution into a graphene oxide solution with the mass concentration of 0.1-20% to obtain a graphene oxide oxalic acid mixed solution; 3) dropwise adding the graphene oxide oxalic acid mixed solution into the rare earth sulfate solution, stirring, filtering and cleaning to obtain a precipitate; 4) dispersing the precipitate obtained in the step 3) into deionized water, adding excessive hydrazine hydrate into the deionized water to reduce graphene oxide into graphene, firing the product obtained after reduction at 400-500 ℃, and keeping the temperature for 2-4 hours to obtain the SCR denitration catalyst.
Description
Technical Field
The invention relates to the technical field of resource utilization of rare earth separation wastewater treatment neutralization residues and preparation of a catalyst for denitration, and particularly relates to a preparation method of a denitration catalyst which takes calcined rare earth separation wastewater treatment neutralization residues as a main component and takes graphene as a carrier.
Background
Graphene is a polymer made of carbon atoms in sp2The two-dimensional carbon nanomaterial with the thickness of the hybridized and connected honeycomb monoatomic layer has high specific surface area, excellent heat conduction performance, good mechanical performance and excellent electron transfer capacity due to the unique structure. The synergistic enhancement effect after the graphene and the inorganic material are compounded has great advantages in catalysis, energy storage and conversion, sensors and other applications, but the direct compounding of the graphene and the metal oxide is very difficult. Graphene oxide is an important oxidized derivative of graphene, has oxygen-containing functional groups on the surface, is a non-traditional soft material, and has the characteristics of polymer, colloid, film and amphoteric molecules. Particularly, due to the amphiphilic molecular property of the graphene oxide, the graphene oxide can exist at interfaces like a surfactant and reduce the energy between the interfaces, and due to the amphiphilicity, the graphene oxide can be compounded with most metals and metal oxides to obtain a composite material with excellent performance. The composite material obtained by taking graphene oxide as an ideal carrier mainly has the following two reasonsThe following reasons: one is that it has a large open surface that allows for better dispersion of the load; secondly, the unique electronic characteristic and the excellent mass transfer characteristic of the material can enhance the activity of the load. However, the graphene oxide has poor electric and thermal conductivity, and the application of the graphene oxide is limited.
The special electronic configuration of the rare earth elements endows the nano rare earth material with a plurality of characteristics, such as high specific surface area, quantum effect, excellent photoelectric property and high chemical activity, and can greatly improve the material performance and the application range. However, the preparation of rare earth oxides is difficult to simultaneously consider crystallinity and dispersibility, and a plurality of unique properties cannot be expressed.
Disclosure of Invention
The invention aims to provide a preparation method of an SCR denitration catalyst, which is characterized in that the SCR denitration catalyst is prepared from rare earth oxalic acid wastewater treatment neutralization slag and graphene, various resources in the rare earth oxalic acid wastewater treatment neutralization slag can be comprehensively recovered, rare earth metal oxide in the rare earth oxalic acid wastewater treatment neutralization slag is loaded on the graphene to form the efficient SCR denitration catalyst, so that the waste is recycled, and the denitration efficiency can reach 70-95%.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing an SCR denitration catalyst, the method comprising the steps of:
1) dissolving the rare earth oxalic acid wastewater treatment neutralization slag by using sulfuric acid, wherein calcium-based components in the rare earth oxalic acid wastewater treatment neutralization slag form precipitates in a calcium sulfate form, and converting rare earth into sulfuric acid rare earth to enter a solution; after the precipitation conversion is finished, adding concentrated sulfuric acid to ensure that the mass concentration of sulfuric acid in the solution is 2.5-10%, and then separating calcium sulfate precipitation from a sulfuric acid rare earth solution while the solution is hot;
2) adding a saturated oxalic acid solution into a graphene oxide solution with the mass concentration of 0.1-20% to obtain a graphene oxide oxalic acid mixed solution;
3) dropwise adding the graphene oxide oxalic acid mixed solution into the rare earth sulfate solution, stirring, filtering and cleaning to obtain a precipitate;
4) dispersing the precipitate obtained in the step 3) into deionized water, adding excessive hydrazine hydrate into the deionized water to reduce graphene oxide into graphene, firing the product obtained after reduction at 400-500 ℃, and keeping the temperature for 2-4 hours to obtain the SCR denitration catalyst.
Preferably, in the step 1), the dosage of the sulfuric acid is 2.2 to 2.6 times of the theoretical molar mass of calcium in the rare earth oxalic acid wastewater treatment neutralization slag, the precipitation conversion temperature is 75 to 85 ℃, and the precipitation conversion time is 50 to 80 min.
Preferably, in the step 1), the amount of the saturated oxalic acid solution is calculated according to the molar weight of the oxalic acid which is 1-2 times of the molar weight of the sulfuric acid in the rare earth sulfate solution.
Preferably, the graphene oxide is prepared by a Brodie method, a Staudenmaier method or a Hummers method.
Graphene oxide is mainly prepared by peeling graphite oxide, and there are three main preparation methods: the Brodie method, Staudenmier method and Hummers method. The Hummers method has relatively good timeliness and relatively safe preparation process, and is the most commonly used method at present. The method comprises the steps of carrying out oxidation reaction on potassium permanganate in concentrated sulfuric acid and graphite powder to obtain brown graphite flakes with derived carboxylic acid groups on the edges and mainly phenolic hydroxyl groups and epoxy groups on the surfaces, and carrying out ultrasonic or high-shear vigorous stirring on a graphite flake layer to strip the graphite flakes into graphene oxide, thereby forming a stable light brown single-layer graphene oxide suspension in water.
The graphene oxide used in the present invention is commercially available or can be prepared by a known method.
The rare earth separation wastewater treatment neutralization slag in the invention is the rare earth oxalic acid wastewater lime neutralization slag generated by neutralizing rare earth oxalic acid wastewater by lime; wherein the rare earth oxalic acid wastewater is high-concentration acidic wastewater generated by separating rare earth by an oxalic acid precipitation method. The rare earth separation wastewater treatment neutralization slag belongs to general class I industrial solid waste, and comprises the main chemical components of calcium oxalate, rare earth hydroxide, calcium hydroxide, ferric hydroxide, aluminum hydroxide and the like, wherein the specific contents are shown in Table 1. In the prior art, no good resource utilization method for the rare earth separation wastewater treatment neutralization slag exists.
TABLE 1 rare earth metal oxide content in the rare earth oxalic acid wastewater neutralization residue
According to a preferred embodiment of the present invention, a preparation method of an SCR denitration catalyst includes the steps of:
dissolving and precipitating neutralization slag:
and dissolving the neutralized slag by using sulfuric acid, wherein the calcium-based component forms a precipitate in the form of calcium sulfate, and the rare earth is converted into sulfuric acid rare earth and enters the solution. The dosage of the sulfuric acid is 2.2-2.6 times of the theoretical molar mass of calcium in the neutralized slag, the initial mass concentration of the sulfuric acid is 30-40%, the precipitation conversion temperature is 75-85 ℃, the precipitation conversion time is 50-80min, the stirring speed is 600r/min, after the precipitation conversion is finished, 98% concentrated sulfuric acid is used for supplementing 2.5-10% of the mass concentration of the sulfuric acid (the excessive sulfuric acid in the solution is ensured, so that the complete dissolution is realized and the separation of rare earth and calcium is realized), the precipitate and the solution are separated while hot, the precipitate is washed by water and then dried to obtain calcium sulfate, and the rare earth sulfate solution is separated out to obtain the solution A.
Preparing a graphene/metal oxide composite material:
preparing a graphene oxide solution with the mass concentration of 0.1-20%, and adding a certain amount of saturated oxalic acid solution into the graphene oxide solution, wherein the mole number of the oxalic acid is 1-2 times that of sulfuric acid, so as to form a solution B. The solution B is slowly dropped into the solution A dropwise, and stirring is carried out continuously. And (3) filtering and cleaning the obtained precipitate, dispersing the precipitate into deionized water under the action of ultrasonic waves, and simultaneously adding excessive hydrazine hydrate to ensure complete reduction so as to reduce the graphene oxide in the precipitate into graphene. And (3) burning the product obtained after reduction at 450 ℃ and preserving heat for 3h to obtain the required graphene/rare earth metal oxide composite material, wherein the graphene/rare earth metal oxide composite material is used as an SCR denitration catalyst.
The SCR denitration catalyst is prepared by performing chemical conversion, dissolution, precipitation, separation and the like on rare earth wastewater treatment neutralization residues and graphene oxide, and the product is graphene oxide or graphene loaded with rare earth metal oxide (when the graphene oxide or the graphene oxide is completely reduced).
Based on the characteristic of graphene oxide amphiprotic molecules, graphene oxide is used as a carrier to obtain a graphene oxide metal oxide composite material, and the graphene oxide metal oxide composite material is subjected to subsequent reduction treatment to obtain the graphene composite material. The use of graphene in catalysis, energy storage and conversion is improved/enhanced by forming a composite with the graphene. Meanwhile, due to the special properties of the graphene and the rare earth material, other properties are further endowed to the rare earth oxide/graphene nano composite material. The composite material increases the surface area of the catalyst and enhances the catalytic properties of the metal oxide. The prepared graphene/metal oxide composite material is used as an SCR denitration catalyst, denitration reaction is carried out in a temperature range of 280 plus 400 ℃, and the denitration efficiency can reach more than 90%.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
Weighing 50g of rare earth oxalic acid wastewater treatment neutralization slag, dissolving with excessive sulfuric acid, wherein the amount of the sulfuric acid is 2.2 times of the theoretical molar mass of calcium in the rare earth oxalic acid wastewater treatment neutralization slag, calcium-based components in the rare earth oxalic acid wastewater treatment neutralization slag form precipitates in the form of calcium sulfate, and the rare earth is converted into rare earth sulfate to enter a solution; and aging the formed precipitate at 75 ℃ for 60min, stirring at the rotating speed of 600r/min, adding concentrated sulfuric acid after the precipitate conversion is finished to ensure that the mass concentration of sulfuric acid in the solution is 2.5%, and then separating the precipitate from the solution while the precipitate is hot to obtain a sulfuric acid rare earth solution for later use.
Weighing 0.4g of graphene oxide, preparing a graphene oxide solution with the mass concentration of 6%, and adding an excessive saturated oxalic acid solution into the graphene oxide solution, wherein the mole number of the oxalic acid is 1 time of that of sulfuric acid, so as to form a graphene oxide oxalic acid mixed solution. Slowly dropping the graphene oxide and oxalic acid mixed solution into the rare earth sulfate solution drop by drop, and continuously stirring. And (3) filtering and cleaning the obtained precipitate, dispersing the precipitate into deionized water under the action of ultrasonic waves, adding excessive hydrazine hydrate into the deionized water, and burning and preserving heat for 3 hours at 450 ℃ to obtain the required graphene/metal oxide composite material after the reduction of the obtained product.
The prepared graphene/metal oxide composite material is used as an SCR denitration catalyst, denitration reaction is carried out in a temperature range of 350 ℃, and the denitration efficiency can reach more than 90%.
Example 2
Weighing 100g of rare earth oxalic acid wastewater treatment neutralization slag, dissolving with excessive sulfuric acid, wherein the amount of the sulfuric acid is 2.6 times of the theoretical molar mass of calcium in the rare earth oxalic acid wastewater treatment neutralization slag, calcium-based components in the rare earth oxalic acid wastewater treatment neutralization slag form precipitates in the form of calcium sulfate, and the rare earth is converted into rare earth sulfate to enter a solution; and aging the formed precipitate at 85 ℃ for 50min, stirring at the rotating speed of 600r/min, adding concentrated sulfuric acid after the precipitate conversion is finished to ensure that the mass concentration of the sulfuric acid in the solution is 5%, and then separating the precipitate from the solution while the precipitate is hot to obtain a rare earth sulfate solution for later use.
Weighing 1g of graphene oxide, preparing a graphene oxide solution with the mass concentration of 20%, and adding an excessive saturated oxalic acid solution into the graphene oxide solution, wherein the mole number of the oxalic acid is 2 times that of sulfuric acid, so as to form a graphene oxide oxalic acid mixed solution. Slowly dropping the graphene oxide and oxalic acid mixed solution into the rare earth sulfate solution drop by drop, and continuously stirring. And (3) filtering and cleaning the obtained precipitate, dispersing the precipitate into deionized water under the action of ultrasonic waves, adding excessive hydrazine hydrate into the deionized water, and burning and preserving heat for 2 hours at 500 ℃ to obtain the required graphene/metal oxide composite material after the reduction of the obtained product.
The prepared graphene/metal oxide composite material is used as an SCR denitration catalyst, denitration reaction is carried out at the temperature range of 400 ℃, and the denitration efficiency can reach more than 95%.
Example 3
Weighing 80g of rare earth oxalic acid wastewater treatment neutralization slag, dissolving with excessive sulfuric acid, wherein the amount of the sulfuric acid is 2.5 times of the theoretical molar mass of calcium in the rare earth oxalic acid wastewater treatment neutralization slag, calcium-based components in the rare earth oxalic acid wastewater treatment neutralization slag form precipitates in the form of calcium sulfate, and the rare earth is converted into rare earth sulfate to enter a solution; aging the formed precipitate at 80 ℃ for 80min, stirring at the rotating speed of 600r/min, adding concentrated sulfuric acid after the precipitation conversion is finished to ensure that the mass concentration of the sulfuric acid in the solution is 10%, and then separating the precipitate from the solution while the precipitate is hot to obtain a rare earth sulfate solution for later use.
Weighing 0.8g of graphene oxide, preparing a graphene oxide solution with the mass concentration of 0.1%, and adding an excessive saturated oxalic acid solution into the graphene oxide solution, wherein the mole number of the oxalic acid is 1.5 times that of sulfuric acid, so as to form a graphene oxide-oxalic acid mixed solution. Slowly dropping the graphene oxide and oxalic acid mixed solution into the rare earth sulfate solution drop by drop, and continuously stirring. And (3) filtering and cleaning the obtained precipitate, dispersing the precipitate into deionized water under the action of ultrasonic waves, adding excessive hydrazine hydrate into the deionized water, and burning and preserving heat for 4 hours at 400 ℃ to obtain the required graphene/metal oxide composite material after the reduction of the obtained product.
The prepared graphene/metal oxide composite material is used as an SCR denitration catalyst, denitration reaction is carried out at the temperature range of 280 ℃, and the denitration efficiency can reach more than 93%.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A method of preparing an SCR denitration catalyst, the method comprising the steps of:
1) dissolving the rare earth oxalic acid wastewater treatment neutralization slag by using sulfuric acid, precipitating and converting; after the precipitation conversion is finished, adding concentrated sulfuric acid to enable the mass concentration of sulfuric acid in the solution to be 2.5% -10%, and then separating calcium sulfate precipitation from the sulfuric acid rare earth solution;
2) adding a saturated oxalic acid solution into a graphene oxide solution with the mass concentration of 0.1-20% to obtain a graphene oxide oxalic acid mixed solution;
3) dropwise adding the graphene oxide oxalic acid mixed solution into the rare earth sulfate solution, stirring, filtering and cleaning to obtain a precipitate;
4) dispersing the precipitate obtained in the step 3) into deionized water, adding excessive hydrazine hydrate into the deionized water to reduce graphene oxide into graphene, firing the product obtained after reduction at 400-500 ℃, and keeping the temperature for 2-4 hours to obtain the SCR denitration catalyst.
2. The preparation method according to claim 1, wherein in the step 1), the dosage of the sulfuric acid is 2.2 to 2.6 times of the theoretical molar mass of calcium in the neutralized slag in the rare earth oxalic acid wastewater treatment, the precipitation conversion temperature is 75 to 85 ℃, and the precipitation conversion time is 50 to 80 min.
3. The method according to claim 1, wherein the amount of the saturated oxalic acid solution used in step 1) is calculated by the molar amount of oxalic acid being 1 to 2 times the molar amount of sulfuric acid in the rare earth sulfate solution.
4. The preparation method of claim 1, wherein the graphene oxide is prepared by a Brodie method, a Staudenmaier method or a Hummers method.
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Application publication date: 20210907 |