CN110669068B - Method for recycling waste zirconium balls and preparing combustion catalyst - Google Patents
Method for recycling waste zirconium balls and preparing combustion catalyst Download PDFInfo
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- CN110669068B CN110669068B CN201911068592.XA CN201911068592A CN110669068B CN 110669068 B CN110669068 B CN 110669068B CN 201911068592 A CN201911068592 A CN 201911068592A CN 110669068 B CN110669068 B CN 110669068B
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 98
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940095064 tartrate Drugs 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 230000004913 activation Effects 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 13
- JBXGQAYHMVWZED-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;nitric acid Chemical compound O[N+]([O-])=O.OC(=O)C(O)C(O)C(O)=O JBXGQAYHMVWZED-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 14
- 235000002906 tartaric acid Nutrition 0.000 claims description 14
- 239000011975 tartaric acid Substances 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 239000010431 corundum Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009993 causticizing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- FLMUKHGPBVFJLB-UHFFFAOYSA-N [Zr].[Pb].C(C(O)C(O)C(=O)O)(=O)O Chemical compound [Zr].[Pb].C(C(O)C(O)C(=O)O)(=O)O FLMUKHGPBVFJLB-UHFFFAOYSA-N 0.000 abstract 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 20
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 20
- 238000005303 weighing Methods 0.000 description 15
- AYPZCTCULRIASE-ZVGUSBNCSA-L [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] Chemical compound [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] AYPZCTCULRIASE-ZVGUSBNCSA-L 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003754 zirconium Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 carboxyl hydrogen Chemical compound 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- IUZQDDUHWOGGSM-UHFFFAOYSA-H C(=O)([O-])C(O)C(O)C(=O)[O-].[Pb+2].[Zr+4].C(=O)([O-])C(O)C(O)C(=O)[O-].C(=O)([O-])C(O)C(O)C(=O)[O-] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Pb+2].[Zr+4].C(=O)([O-])C(O)C(O)C(=O)[O-].C(=O)([O-])C(O)C(O)C(=O)[O-] IUZQDDUHWOGGSM-UHFFFAOYSA-H 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/44—Lead
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of resource circulation and material engineering, and particularly discloses a method for recycling waste zirconium balls and preparing a combustion catalyst. The method specifically comprises the steps of taking waste zirconium balls generated in the grinding industry as raw materials, adding lead oxide into a tartaric acid-nitric acid mixed acid system, carrying out ball milling activation synthesis, carrying out reactions such as acid dissolution decomposition and chemical combination, and adding sodium hydroxide for causticization so as to convert the waste zirconium balls into lead zirconium tartrate; and then the pure tartaric acid lead zirconium is prepared by rinsing lead and vacuum drying. The invention takes waste zirconium balls which are difficult to treat and utilize as a zirconium source and an activation medium, prepares the functional material combustion catalyst lead zirconium tartrate by the design of a synthesis system, and realizes the recycling and value-added utilization of secondary resources.
Description
Technical Field
The invention belongs to the technical field of resource circulation and material engineering, and particularly relates to a method for recycling waste zirconium balls and preparing a combustion catalyst.
Background
The zirconia ball has the advantages of high strength, high toughness, good wear resistance, high temperature resistance, corrosion resistance, no magnetic permeability, electric insulation and the like, and the strength and the hardness of the zirconia ball are almost unchanged at the temperature higher than 500 ℃, so the zirconia ball is widely used as a ball milling medium in powder engineering and bearing materials. However, the ball milling impact for a long time can cause the problems of surface damage, cracks and pits and volume reduction of the ball body, so that the ball body can not be used and can not be discarded. Each large powder enterprise produces certain waste zirconium balls, and due to chemical inertness and high hardness, the waste zirconium balls are difficult to recover, so that an economic and effective utilization way is not available at present. But the chemical composition of the zirconium oxide is still pure zirconium oxide, and the zirconium oxide almost contains no impurities, and is an important zirconium resource.
The lead zirconium tartrate is an important fuel stabilizer, has important application in fuel combustion and rocket solid propellant, but is difficult to synthesize. Patent CN101531587A discloses a lead-zirconium tartrate double metal salt and a preparation method and application thereof, wherein the lead-zirconium tartrate double metal salt is prepared by pre-synthesizing lead tartrate and adding soluble zirconium salt for coprecipitation, both the lead salt and the zirconium salt need to be prepared in advance, and the prepared lead-zirconium tartrate has a good inhibition effect on unstable combustion of a solid propellant. Other preparation methods are not reported yet.
The invention provides a method for recycling waste zirconium balls and preparing a combustion catalyst, which comprises the steps of utilizing the waste zirconium balls as zirconium sources, adding lead oxide, dissolving the zirconium balls in a mixed acid system of tartaric acid and nitric acid by utilizing the ball milling activation effect of the zirconium balls, reacting with the lead oxide, causticizing and transforming, and further reacting to generate lead zirconium tartrate. Although the surface of the waste zirconium balls has defects and can be broken or pulverized, zirconium is a raw material required by the synthesis reaction, so that the pollution is not caused, and the reaction is accelerated. Therefore, the invention takes waste zirconium balls and cheap lead oxide as raw materials, cancels the preparation of soluble lead and zirconium salt, synthesizes combustion catalyst zirconium lead tartrate through ball milling activation, and realizes the resource recovery and value-added manufacture of the waste.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for effectively recycling waste zirconium balls and preparing a combustion catalyst of lead-zirconium tartrate, wherein the waste zirconium balls generated in the grinding industry are used as raw materials, lead oxide is added into a mixed acid system of tartaric acid and nitric acid to carry out ball milling activation reaction, causticization synthesis, lead rinsing and vacuum drying are carried out, and the combustion catalyst of lead-zirconium tartrate is prepared.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for recycling waste zirconium balls and preparing a combustion catalyst comprises the following steps:
s1, ball milling activation synthesis: taking waste zirconium balls as raw materials, adding tartaric acid-nitric acid binary mixed acid synthetic solution and lead oxide, carrying out ball milling reaction, adding sodium hydroxide after reacting for a period of time, continuing ball milling reaction, causticizing and transforming to generate lead zirconium tartrate, then separating the waste zirconium balls and slurry, carrying out liquid-solid separation on the obtained slurry to obtain precipitate and decomposition liquid containing the lead zirconium tartrate, and returning the decomposition liquid to the step S1 for circulation;
s2, rinsing lead: rinsing the precipitate obtained in the step S1 by using an acid solvent to remove unreacted lead;
s3, vacuum drying: vacuum drying the rinsed precipitate in the step S2 to obtain a lead zirconium tartrate product, so as to prevent the lead zirconium tartrate product from oxidative decomposition;
wherein: in step S1, the liquid-solid ratio of the lead oxide to the tartaric acid-nitric acid mixed acid synthetic liquid is 10-50: 1.
The invention is based on waste reutilization, fully utilizes the physicochemical properties of the raw materials, scientifically designs the ingredients and adopts the production process to prepare the lead-zirconium tartrate with high added value.
In step S1, performing ball milling activation synthesis using waste zirconium balls as raw materials, adding lead oxide into a tartaric acid-nitric acid binary mixed acid synthetic solution, performing ball milling reaction, and performing acid dissolution decomposition, direct combination and other reactions, wherein the lead oxide and tartaric acid consume carboxyl hydrogen in tartaric acid under the ball milling action and combine with lead to generate lead tartrate, and the nitric acid and zirconium balls generate zirconyl nitrate under the ball milling action; sodium hydroxide is added in the later stage to remove hydroxyl hydrogen in the lead tartrate structure, and H-O bonds are broken, so that the ZrO (NO) and the ZrO (NO) are bonded 3 ) 2 Forming Zr-O coordination bonds, carrying out ball milling reaction combination to obtain slurry containing lead zirconium tartrate insoluble matters, and carrying out liquid-solid separation. The method makes full use of the physical and chemical characteristics of the waste zirconium balls, such as surface defects and pure zirconium oxide composition, and the damaged zirconium balls are more favorable for zirconium erosion and dissolution reaction than the smooth surfaces of fresh zirconium balls, and the reaction schematic diagram of the whole process is shown in figure 1.
Next, step S2 is performed to rinse the lead and wash away the unreacted lead oxide to ensure the purity of the lead zirconium tartrate. The excess lead oxide can be dissolved and removed by using acetic acid by utilizing the high dissolution characteristic of the lead acetate. The weak acidity of acetic acid does not destroy the structure of lead zirconium tartrate.
And finally, step S3, drying the rinsed sample in vacuum to obtain a lead zirconium tartrate product, wherein the drying is carried out under vacuum and low temperature conditions to prevent oxidative decomposition of tartaric acid groups, which is beneficial to structural stability.
Preferably, before step S1, the waste zirconium balls are subjected to surface cleaning, specifically: soaking the waste zirconium balls in a dilute hydrochloric acid solution to remove impurities for a period of time so as to remove the impurities brought in the ball milling process, and washing and drying the waste zirconium balls by water.
Preferably, the waste zirconium balls are from the grinding industry, the components of the waste zirconium balls are zirconia, and the diameter of the waste zirconium balls is less than 10 cm.
Preferably, the waste zirconium balls are washed before step S1, further preferably, the washing is performed in a dilute hydrochloric acid solution, further preferably, the dilute hydrochloric acid solution has a pH of 2, and the soaking and washing time is 24 hours.
Preferably, the ball milling activation synthesis of step S1 is performed in a ball milling tank, and the material is one of corundum, nylon or polyurethane. Further preferably, the ball mill pot is a corundum pot.
Preferably, the ball milling activation synthesis time of the step S1 is 5-20 h, and the ball liquid ratio is 1: 1 to 5, and a rotation speed of 40 to 200 rpm. Further preferably, the rotation speed is 80-150 rpm.
Preferably, in step S1, the tartaric acid concentration in the tartaric acid-nitric acid binary mixed acid synthetic solution is 50-200 g/L, and the nitric acid concentration is 20-50 g/L.
Preferably, in step S1, the mass of the added sodium hydroxide is 0.68 to 0.80 times of the mass of the tartaric acid, and the ball milling reaction is continued for 0.5 to 2 hours after the sodium hydroxide is added. Further preferably, the addition amount of the sodium hydroxide is 0.68 to 0.73 times.
Preferably, in step S2, the rinsing of the lead is performed in a stirred reactor for 0.5 to 3 hours at a rotation speed of 30 to 100rpm and a liquid-solid ratio of 4 to 10: 1.
preferably, in step S2, the acidic solvent for rinsing the lead is acetic acid, and further preferably, the concentration of the acetic acid is 10 to 45 g/L; still more preferably, the concentration of acetic acid is 20 to 40 g/L.
Preferably, in step S3, the temperature of the vacuum drying is 30 to 60 ℃, the vacuum degree is 5 to 100Pa, and the time is 24 to 48 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for recycling the waste zirconium balls and preparing the combustion catalyst realizes resource utilization of zirconium balls which are difficult to treat wastes, creatively utilizes physical and chemical characteristics of the waste zirconium balls with surface defects and pure zirconium oxide compositions, generates a series of corrosion, dissolution and combination reactions through the synergistic effect of dissolution of a tartaric acid-nitric acid mixed acid system and ball milling activation of the zirconium balls, finally generates lead-zirconium tartrate, has the conversion rate of zirconium of over 95 percent, cancels the chemical synthesis of soluble lead salt and zirconium salt in advance, and has obvious cleaning and resource characteristics.
(2) The method for recycling the waste zirconium balls and preparing the combustion catalyst has the advantages that the high-value combustion catalyst lead zirconium tartrate is efficiently synthesized, the high-inertia zirconium oxide participates in the chemical combination reaction through the liquid phase ball milling activation effect, and the product layer on the particle surface can be continuously stripped through ball milling, so that the reaction is continuously carried out, and the purpose of efficient synthesis is achieved.
Drawings
FIG. 1 is a reaction diagram of the ball milling activation synthesis process of step S1 in the method for recycling waste zirconium balls and preparing a combustion catalyst.
FIG. 2 is a process flow diagram of a method for recycling waste zirconium balls and preparing a combustion catalyst according to the present invention.
FIG. 3 is a drawing of a sample of waste zirconium balls used in the examples of the present invention.
FIG. 4 is an XRD analysis pattern of the lead zirconium tartrate product of example 1 of the present invention.
FIG. 5 is an SEM image of the lead zirconium tartrate product of example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The composition of the waste zirconium balls used as raw materials in the embodiment of the invention is zirconium dioxide, the diameter of each waste zirconium ball is less than 10cm, the waste zirconium balls are distributed according to the equal proportion of the size balls, and the real object diagram is shown in figure 3.
Example 1
The embodiment provides a method for recycling waste zirconium balls and preparing a combustion catalyst, a process flow diagram of which is shown in figure 2, and the method specifically comprises the following steps:
s1, ball milling activation synthesis: weighing 1000g of zirconium balls and 80g of PbO, adding the zirconium balls and 80g of PbO into a corundum ball milling tank, weighing 2000mL of tartaric acid-nitric acid binary mixed acid synthetic liquid, adding the tartaric acid binary mixed acid synthetic liquid into the corundum ball milling tank, wherein the concentration of tartaric acid is 100g/L and the concentration of nitric acid is 35g/L, starting ball milling, reacting at the speed of 80rpm for 10h, then adding 140g of NaOH, continuously reacting for 1h, separating the zirconium balls and slurry, washing the zirconium balls, weighing 984.4g of the zirconium balls, and obtaining the dissolution rate of 1.56%. And (4) carrying out liquid-solid separation on the slurry, wherein all solids enter the rinsing lead of the next step, and the decomposed liquid can return to the step S1 for circulation.
S2, rinsing lead: according to the liquid-solid ratio of 8: and 1, adding 1110mL of 20g/L acetic acid solution to rinse the solid obtained in the step S1, setting the rotation speed to be 60rpm, stirring for 2 hours, stopping stirring, and performing liquid-solid separation to obtain filter residue.
S3, vacuum drying: and (4) putting the filter residue obtained in the step (S2) into a vacuum drying oven, drying for 24 hours at 50Pa and 40 ℃, and packaging to obtain the final lead zirconium tartrate catalyst. The weight of the lead tartrate is 139.31g, the conversion rates of lead and zirconium are calculated to be 95.31% and 99.02% respectively, and the obtained lead tartrate is analyzed and characterized, the carbon content is 11.94%, and the theoretical value is close to 11.78%; as shown in FIGS. 4 and 5, the XRD and SEM analyses showed that the synthesized product was relatively pure, all diffraction peaks were lead zirconium tartrate, which was agglomerated together in the form of flaky irregular particles having a particle size of 5 μm or less.
Example 2
The embodiment provides a method for recycling waste zirconium balls and preparing a combustion catalyst, a process flow diagram of which is shown in figure 2, and the method specifically comprises the following steps:
s1, ball milling activation synthesis: weighing 1000g of zirconium balls and 80g of PbO, adding the zirconium balls and the 80g of PbO into a corundum ball milling tank, weighing 2800mL of synthetic solution, adding the synthetic solution into the corundum ball milling tank, wherein the concentration of tartaric acid is 75g/L and the concentration of nitric acid is 26g/L, starting ball milling, reacting at the speed of 90rpm for 6h, adding 143g of NaOH, continuing to react for 2h, separating the zirconium balls and slurry, washing the zirconium balls, weighing 982.7g of the zirconium balls, and obtaining the dissolution rate of 1.73%. And (4) carrying out liquid-solid separation on the slurry, wherein all the solid matters enter the rinsing lead of the next step, and the decomposition liquid can return to the step S1 for circulation.
S2, rinsing lead: according to the liquid-solid ratio of 6: 1, adding 950mL of acetic acid solution with the concentration of 30g/L to rinse the solid obtained in the step S1, setting the rotation speed to be 80rpm, stirring for 2 hours, stopping stirring, and performing liquid-solid separation to obtain filter residue.
S3, vacuum drying: and (4) putting the filter residue obtained in the step (S2) into a vacuum drying oven, drying for 24 hours at the temperature of 40 ℃ under 20Pa, and packaging to obtain the final lead zirconium tartrate catalyst. The weight of the lead tartrate was 141.27g, the conversion rates of lead and zirconium were calculated to be 96.65% and 99.33%, respectively, and the obtained lead tartrate was characterized by analysis to have a carbon content of 11.76%, which was close to the theoretical value of 11.78%.
Example 3
The embodiment provides a method for recycling waste zirconium balls and preparing a combustion catalyst, a process flow diagram of which is shown in figure 2, and the method specifically comprises the following steps:
s1, ball-milling activation synthesis: weighing 1000g of zirconium balls and 80g of PbO, adding the zirconium balls and 80g of PbO into a corundum ball milling tank, weighing 4000mL of synthetic liquid, adding the synthetic liquid into the corundum ball milling tank, wherein the concentration of tartaric acid is 150g/L and the concentration of nitric acid is 20g/L, starting ball milling, reacting at the speed of 50rpm for 14h, adding 400g of NaOH, continuously reacting for 1.5h, separating the zirconium balls and slurry, washing the zirconium balls, weighing 980.7g of the zirconium balls, and obtaining the dissolution rate of 1.93%. And (4) carrying out liquid-solid separation on the slurry, and completely carrying out the solid matter on the lead rinsing in the next step.
S2, rinsing lead: according to the liquid-solid ratio of 10: and 1, adding 1420mL of 10g/L acetic acid solution to rinse the solid obtained in the step S1, setting the rotation speed to be 90rpm, stirring for 1 hour, stopping stirring, and performing liquid-solid separation to obtain filter residue.
S3, vacuum drying: and (4) putting the filter residue obtained in the step (S2) into a vacuum drying oven, drying for 48 hours at 10Pa and 40 ℃, and packaging to obtain the final lead zirconium tartrate catalyst. The weight of the lead tartrate was measured to be 137.24g, the conversion rates of lead and zirconium were calculated to be 93.89% and 97.05%, respectively, and the obtained lead tartrate was characterized by analysis to have a carbon content of 11.94%, which was close to the theoretical value of 11.78%.
Example 4
The embodiment provides a method for recycling waste zirconium balls and preparing a combustion catalyst, a process flow diagram of which is shown in figure 2, and the method specifically comprises the following steps:
s1, ball-milling activation synthesis: weighing 1000g of zirconium balls and 120g of PbO, adding the zirconium balls and the 120g of PbO into a corundum ball milling tank, weighing 3000mL of synthetic solution, adding the synthetic solution into the corundum ball milling tank, wherein the concentration of tartaric acid is 170g/L and the concentration of nitric acid is 40g/L, starting ball milling, reacting at the speed of 180rpm for 6h, adding 382g of NaOH, continuously reacting for 1.5h, separating the zirconium balls and slurry, washing the zirconium balls, weighing 976.6g of the zirconium balls, and obtaining the dissolution rate of 2.34%. And (4) carrying out liquid-solid separation on the slurry, and completely carrying out the solid matter on the lead rinsing in the next step.
S2, rinsing lead: according to the liquid-solid ratio of 5: and 1, adding 975mL of acetic acid solution with the concentration of 30g/L to rinse the solid obtained in the step S1, setting the rotation speed to be 80rpm, stirring for 1.5h, stopping stirring, and performing liquid-solid separation to obtain filter residue.
S3, vacuum drying: and (5) putting the filter residue obtained in the step S2 into a vacuum drying oven, drying for 48 hours at the temperature of 50 ℃ under the pressure of 10Pa, and packaging to obtain the final lead zirconium tartrate catalyst. The weight of the lead tartrate was 207.68g, and the conversion rates of lead and zirconium were calculated to be 94.27% and 96.11%, respectively, and the obtained lead tartrate was characterized by analysis and had a carbon content of 11.13%.
Example 5
The embodiment provides a method for recycling waste zirconium balls and preparing a combustion catalyst, a process flow diagram of which is shown in figure 2, and the method specifically comprises the following steps:
s1, ball milling activation synthesis: weighing 1000g of zirconium balls and 120g of PbO, adding the zirconium balls and the 120g of PbO into a corundum ball milling tank, weighing 1300mL of synthetic liquid, adding the synthetic liquid into the corundum ball milling tank, wherein the concentration of tartaric acid is 190g/L and the concentration of nitric acid is 45g/L, starting ball milling, reacting for 8h at the speed of 200rpm, adding 178g of NaOH, continuously reacting for 1h, separating the zirconium balls and slurry, washing the zirconium balls, weighing 987.2g of zirconium balls, and obtaining the dissolution rate of 1.28%. And (4) carrying out liquid-solid separation on the slurry, and completely carrying out the solid matter on the lead rinsing in the next step.
S2, rinsing lead: according to the liquid-solid ratio of 5: and 1, adding 980mL of acetic acid solution with the concentration of 45g/L to rinse the solid obtained in the step S1, setting the rotation speed to be 20rpm, stirring for 3 hours, stopping stirring, and performing liquid-solid separation to obtain filter residue.
S3, vacuum drying: and (4) putting the filter residue obtained in the step (S2) into a vacuum drying oven, drying for 48 hours at the temperature of 30 ℃ under 100Pa, and packaging to obtain the final lead zirconium tartrate catalyst. The weight of the lead tartrate was 205.33g, and the conversion rates of lead and zirconium were calculated to be 93.77% and 97.16%, respectively, and the obtained lead tartrate was characterized by analysis and had a carbon content of 10.89%. .
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (12)
1. A method for recycling waste zirconium balls and preparing a combustion catalyst is characterized by comprising the following steps:
s1, ball-milling activation synthesis: taking waste zirconium balls as raw materials, adding tartaric acid-nitric acid binary mixed acid synthetic solution and lead oxide, carrying out ball milling reaction, adding sodium hydroxide after reacting for a period of time, continuing ball milling reaction, causticizing and transforming to generate lead zirconium tartrate, then separating the waste zirconium balls and slurry, carrying out liquid-solid separation on the obtained slurry to obtain precipitate and decomposition liquid containing the lead zirconium tartrate, and returning the decomposition liquid to the step S1 for circulation;
s2, rinsing lead: rinsing the precipitate obtained in the step S1 by using an acid solvent to remove unreacted lead;
s3, vacuum drying: vacuum drying the rinsed precipitate in the step S2 to obtain a lead zirconium tartrate product;
wherein: in step S1, the liquid-solid ratio of the lead oxide and the tartaric acid-nitric acid mixed acid synthetic solution is 10: 1-50: 1; the ball milling activation synthesis time is 5-20 h, and the ball liquid ratio is 1: 1 to 5, and a rotation speed of 40 to 200 rpm.
2. The method of claim 1, wherein the waste zirconium balls are from the grinding industry and comprise zirconia, and the diameter of the waste zirconium balls is less than 10 cm.
3. The method for recycling the waste zirconium balls and preparing the combustion catalyst as claimed in claim 1 or 2, wherein the waste zirconium balls are cleaned before step S1.
4. The method according to claim 3, wherein the washing is performed in a dilute hydrochloric acid solution.
5. The method for recycling waste zirconium balls and preparing a combustion catalyst as claimed in claim 4, wherein the dilute hydrochloric acid solution has a pH of 2 and the soaking and cleaning time is 24 h.
6. The method of claim 1, wherein the ball milling activation synthesis of step S1 is performed in a ball milling pot made of one of corundum, nylon or polyurethane.
7. The method for recycling waste zirconium balls and preparing a combustion catalyst as claimed in claim 1, wherein in step S1, the tartaric acid concentration in the tartaric acid-nitric acid mixed binary acid synthetic fluid is 50-200 g/L, and the nitric acid concentration is 20-50 g/L.
8. The method for recycling the waste zirconium balls and preparing the combustion catalyst as claimed in any one of claims 1, 2 and 4 to 7, wherein in the step S1, the mass of the added sodium hydroxide is 0.68 to 0.80 times of the mass of the tartaric acid, and the ball milling reaction is continued for 0.5 to 2 hours after the sodium hydroxide is added.
9. The method for recycling waste zirconium balls and preparing a combustion catalyst as claimed in claim 1, wherein in step S2, the rinsing lead is performed in a stirred reactor for 0.5-3 h at a rotation speed of 30-100 rpm with a liquid-solid ratio of 4-10: 1.
10. the method for recycling waste zirconium balls and preparing a combustion catalyst as claimed in claim 1 or 9, wherein in step S2, the acid solvent for rinsing lead is acetic acid.
11. The method for recycling waste zirconium balls and preparing a combustion catalyst as claimed in claim 10, wherein the concentration of acetic acid is 10-45 g/L.
12. The method for recycling the waste zirconium balls and preparing the combustion catalyst as claimed in claim 1, wherein in step S3, the temperature of the vacuum drying is 30-60 ℃, the vacuum degree is 5-100 Pa, and the time is 24-48 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531587A (en) * | 2009-03-04 | 2009-09-16 | 西安近代化学研究所 | Zirconium lead tartrate double metal salt, preparation method and application thereof |
| CN108083332A (en) * | 2017-12-25 | 2018-05-29 | 山东磊宝锆业科技股份有限公司 | It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid |
| CN108083333A (en) * | 2017-12-25 | 2018-05-29 | 山东磊宝锆业科技股份有限公司 | It is a kind of to be given up the method that zirconium prepares zirconium aluminium composite granule using solid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531587A (en) * | 2009-03-04 | 2009-09-16 | 西安近代化学研究所 | Zirconium lead tartrate double metal salt, preparation method and application thereof |
| CN108083332A (en) * | 2017-12-25 | 2018-05-29 | 山东磊宝锆业科技股份有限公司 | It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid |
| CN108083333A (en) * | 2017-12-25 | 2018-05-29 | 山东磊宝锆业科技股份有限公司 | It is a kind of to be given up the method that zirconium prepares zirconium aluminium composite granule using solid |
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