CN111876604A - Process method for treating and utilizing sulfuric acid catalyst prepared from waste vanadium-silicon system - Google Patents
Process method for treating and utilizing sulfuric acid catalyst prepared from waste vanadium-silicon system Download PDFInfo
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- CN111876604A CN111876604A CN202010767395.3A CN202010767395A CN111876604A CN 111876604 A CN111876604 A CN 111876604A CN 202010767395 A CN202010767395 A CN 202010767395A CN 111876604 A CN111876604 A CN 111876604A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a process method for treating and utilizing a catalyst for preparing sulfuric acid from waste vanadium-silicon series, which comprises the following process steps: 1) performing ultrasonic initial washing, namely taking the waste vanadium-silicon system sulfuric acid preparation catalyst to perform ultrasonic initial washing to obtain a vanadium-silicon system sulfuric acid preparation catalyst after preliminary washing; 2) drying, namely drying the vanadium-silicon system sulfuric acid preparation catalyst subjected to ultrasonic primary washing; 3) crushing and grinding, crushing the dried vanadium-silicon system sulfuric acid preparation catalyst by a crushing device, and crushing the waste vanadium-silicon system sulfuric acid preparation catalyst to more than 150 meshes; 4) acid leaching, namely crushing the waste vanadium-silicon system sulfuric acid preparation catalyst, then putting the crushed waste vanadium-silicon system sulfuric acid preparation catalyst into hydrochloric acid or sulfuric acid solution, simultaneously adding a reducing agent sodium sulfite, and heating and leaching; 5) solid-liquid separation, namely performing solid-liquid separation on the solution subjected to acid leaching treatment; 6) carrying out vanadium precipitation treatment on the separated filtrate to obtain crude vanadium precipitate; 7) dehydrating the obtained crude vanadium precipitate to obtain a calcium vanadate product; 8) and rinsing and dehydrating the separated filter residue to obtain the silicon micropowder.
Description
Technical Field
The invention relates to the technical field of catalyst recovery treatment, in particular to a process method for treating and utilizing a waste vanadium-silicon system sulfuric acid preparation catalyst.
Background
Sulfuric acid is a basic chemical raw material, the sulfuric acid yield of China is the first place in the world, at present, the sulfuric acid is mainly produced by a contact method in China, and a catalyst for oxidizing sulfur dioxide in the process is the key point of production.
The vanadium catalyst used in industry at present is a multi-component catalyst which takes V2O5 as an active component, alkali metal sulfate (K2SO4 or Na2SO4) as a cocatalyst and diatomite as a carrier, and is generally called vanadium-potassium (sodium) -silicon catalyst.
In the past, the waste catalyst is mostly treated by landfill, which wastes resources and pollutes the environment. In recent years, due to the rising price of catalyst raw materials, the recovery of vanadium from sulfuric acid production waste catalysts has generally been regarded as important. The research on the problem is also carried out by the Kentungy company, so that better results are obtained, and if the Kentungy company is put into production in the future, the economic benefit can be improved, and the environmental pollution can be controlled. The technology is designed and applied for the first time in the field of treatment and utilization of vanadium-silicon system sulfuric acid catalyst waste, and can be improved along with the development of a comprehensive utilization process.
The invention is a research project based on the treatment and utilization process of the catalyst for preparing sulfuric acid from waste vanadium-silicon series.
Disclosure of Invention
The invention aims to provide a process method for treating and utilizing a waste vanadium-silicon system sulfuric acid preparation catalyst, which aims to realize the maximum utilization of resources, change waste into valuable (preparing calcium vanadate and silicon micropowder products) and avoid pollution to the environment; and the technical problems of improving the yield, reducing the energy consumption and reducing the cost.
The process method for treating and utilizing the waste vanadium-silicon system sulfuric acid catalyst is realized as follows:
the process method for treating and utilizing the sulfuric acid catalyst prepared from the waste vanadium-silicon system comprises the following process steps:
1) performing ultrasonic initial washing, namely taking the waste vanadium-silicon system sulfuric acid preparation catalyst to perform ultrasonic initial washing to obtain a vanadium-silicon system sulfuric acid preparation catalyst after preliminary washing;
2) drying, namely drying the vanadium-silicon system sulfuric acid preparation catalyst subjected to ultrasonic primary washing;
3) crushing and grinding, crushing the dried vanadium-silicon system sulfuric acid preparation catalyst by a crushing device, and crushing the waste vanadium-silicon system sulfuric acid preparation catalyst to more than 150 meshes;
4) acid leaching, namely crushing the waste vanadium-silicon system sulfuric acid preparation catalyst, then putting the crushed waste vanadium-silicon system sulfuric acid preparation catalyst into hydrochloric acid or sulfuric acid solution, simultaneously adding a reducing agent sodium sulfite, and heating and leaching;
5) solid-liquid separation, namely performing solid-liquid separation on the solution subjected to acid leaching treatment;
6) carrying out vanadium precipitation treatment on the separated filtrate to obtain crude vanadium precipitate;
7) dehydrating the obtained crude vanadium precipitate to obtain a calcium vanadate product;
8) and rinsing and dehydrating the separated filter residue to obtain the silicon micropowder.
Further, in the step 4), adding 8-12 wt% sulfuric acid, adjusting the pH value to 11.5-12.5 at 70-90 ℃, standing for 0.5-1 h, and performing primary filtration.
Further, in the step 4), sulfuric acid with the concentration of 8-12 wt% is continuously added into the filtered solution to adjust the pH value to 9-10, the filter residue obtained by filtering is silicic acid, and the chemical reaction formula is as follows:
Na2SiO3+H2SO4＝H2SiO3+Na2SO4+H2O。
further, in the step 6), Ca2+ is added in the vanadium precipitation process to carry out vanadium precipitation treatment, so as to form a calcium vanadate product.
Further, the CaCl2 added in the step 6) needs to be adjusted to a pH value of 10.8-11.
Further, Ca (OH)2 is added in the step 6), and the ph value is regulated to 7.8-9.3.
Further, the pH value of CaO added in the step 6) needs to be adjusted to 5.1-6.1.
Compared with the prior art, the embodiment of the invention has the following beneficial effects: the complete treatment and utilization process of the sulfuric acid catalyst prepared from the waste vanadium-silicon system can realize the maximum utilization of resources, change waste into valuable (preparing calcium vanadate and silicon micropowder products), and avoid the pollution to the environment; the optimal reaction condition is researched, the yield is improved, the energy consumption is reduced, and the cost is reduced.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 shows a schematic diagram of the process steps provided by an embodiment of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
As shown in fig. 1, the process method for treating and utilizing the waste vanadium-silicon system sulfuric acid catalyst comprises the following process steps:
1) performing ultrasonic initial washing, namely taking the waste vanadium-silicon system sulfuric acid preparation catalyst to perform ultrasonic initial washing to obtain a vanadium-silicon system sulfuric acid preparation catalyst after preliminary washing;
2) drying, namely drying the vanadium-silicon system sulfuric acid preparation catalyst subjected to ultrasonic primary washing;
3) crushing and grinding, crushing the dried vanadium-silicon system sulfuric acid preparation catalyst by a crushing device, and crushing the waste vanadium-silicon system sulfuric acid preparation catalyst to more than 150 meshes;
4) acid leaching, namely crushing the waste vanadium-silicon system sulfuric acid preparation catalyst, then putting the crushed waste vanadium-silicon system sulfuric acid preparation catalyst into hydrochloric acid or sulfuric acid solution, simultaneously adding a reducing agent sodium sulfite, and heating and leaching;
5) solid-liquid separation, namely performing solid-liquid separation on the solution subjected to acid leaching treatment;
6) carrying out vanadium precipitation treatment on the separated filtrate to obtain crude vanadium precipitate;
7) dehydrating the obtained crude vanadium precipitate to obtain a calcium vanadate product;
8) and rinsing and dehydrating the separated filter residue to obtain the silicon micropowder.
Wherein, in the step 4), 8-12 wt% sulfuric acid is added, the pH is adjusted to 11.5-12.5 at 70-90 ℃, and the mixture is kept stand for 0.5-1 h for primary filtration. The Fe (OH)3 and Al (OH)3 impurities are filtered off.
The chemical reaction is as follows:
2NaFe(OH)4+H2SO4＝Na2SO4+2Fe(OH)3+2H2O
2NaAl(OH)4+H2SO4＝Na2SO4+2Al(OH)3+2H2O。
in the step 4), continuously adding 8-12 wt% sulfuric acid into the filtered solution to adjust the pH value to 9-10, wherein the filter residue obtained by filtering is silicic acid, and the chemical reaction formula is as follows:
Na2SiO3+H2SO4＝H2SiO3+Na2SO4+H2O。
in the acid leaching treatment in the step 4), 4-6 times of NaOH solution with the concentration of 60-80 wt% can be added, the solution is heated to 140-150 ℃, and when the solution is soaked for 3-5 hours, TiO2, V2O5, WO3, SiO2, Fe2O3 and Al2O3 are subjected to sodium treatment; wherein, the titanium dioxide in the catalyst reacts with sodium hydroxide to generate sodium metatitanate Na2TiO3, and most of vanadium, silicon and tungsten can react with the sodium hydroxide to generate water-soluble sodium metavanadate NaVO3, sodium silicate Na2SiO3 and sodium tungstate Na2WO 4.
The chemical reaction is as follows:
TiO2+2NaOH＝Na2TiO3↓+H2O
V2O5+2NaOH＝2NaVO3+H2O
WO3+2NaOH＝Na2WO4+H2O
SiO2+2NaOH＝Na2SiO3+H2O
Fe2O3+2NaOH+3H2O＝2NaFe(OH)4
Al2O3+2NaOH+3H2O＝2NaAl(OH)4
in the step 6), Ca2+ is added in the vanadium precipitation process for vanadium precipitation treatment to form a calcium vanadate product.
The CaCl2 added in step 6) is adjusted to a pH value of 10.8-11.
The Ca (OH)2 added in the step 6) needs to be adjusted to a pH value of 7.8-9.3.
The pH value of CaO added in the step 6) needs to be adjusted to 5.1-6.1.
In the invention: 1) the cleaning rate of the waste catalyst reaches more than 98 percent;
2) the leaching rate of vanadium reaches more than 85 percent;
3) the purity of the prepared calcium vanadate reaches more than 90 percent;
4) the purity of the prepared silicon micro powder product reaches more than 99.5 percent.
The waste vanadium-silicon system sulfuric acid catalyst contains impurities such as K2O, SO3, Fe2O3, Al2O3 and the like, and the waste vanadium-silicon system sulfuric acid catalyst needs to be fully cleaned in multiple steps to remove the impurities in the waste vanadium-silicon system sulfuric acid catalyst, and is dried and ground after passing the test. The cleaning mainly comprises processes of ultrasonic initial cleaning, chemical cleaning, ultrasonic fine cleaning, rinsing with clear water and the like, wherein the chemical cleaning is a particularly critical step in the process, and impurities such as potassium oxide, sulfur trioxide, aluminum oxide, iron oxide and the like need to be washed from the waste catalyst, so that the purity of a subsequently prepared product is improved.
In the process of extracting vanadium, acid leaching, solid fineness, acid liquor selection, acid concentration, solid-liquid ratio and reaction temperature and time are all key factors for determining the purity of the finally prepared product and the resource utilization rate. The invention obtains the optimal leaching parameters through a large amount of experimental researches.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
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 protection scope of the present invention.
Claims (7)
1. The process method for treating and utilizing the sulfuric acid catalyst prepared from the waste vanadium-silicon system is characterized by comprising the following process steps:
1) performing ultrasonic initial washing, namely taking the waste vanadium-silicon system sulfuric acid preparation catalyst to perform ultrasonic initial washing to obtain a vanadium-silicon system sulfuric acid preparation catalyst after preliminary washing;
2) drying, namely drying the vanadium-silicon system sulfuric acid preparation catalyst subjected to ultrasonic primary washing;
3) crushing and grinding, crushing the dried vanadium-silicon system sulfuric acid preparation catalyst by a crushing device, and crushing the waste vanadium-silicon system sulfuric acid preparation catalyst to more than 150 meshes;
4) acid leaching, namely crushing the waste vanadium-silicon system sulfuric acid preparation catalyst, then putting the crushed waste vanadium-silicon system sulfuric acid preparation catalyst into hydrochloric acid or sulfuric acid solution, simultaneously adding a reducing agent sodium sulfite, and heating and leaching;
5) solid-liquid separation, namely performing solid-liquid separation on the solution subjected to acid leaching treatment;
6) carrying out vanadium precipitation treatment on the separated filtrate to obtain crude vanadium precipitate;
7) dehydrating the obtained crude vanadium precipitate to obtain a calcium vanadate product;
8) and rinsing and dehydrating the separated filter residue to obtain the silicon micropowder.
2. The process method for treating and utilizing the sulfuric acid catalyst prepared from the waste vanadium-silicon system according to claim 1, wherein in the step 4), the sulfuric acid with the concentration of 8-12 wt% is added, the pH value is adjusted to 11.5-12.5 at 70-90 ℃, the mixture is kept stand for 0.5-1 h, and primary filtration is performed.
3. The process method for treating and utilizing the sulfuric acid catalyst prepared from the waste vanadium-silicon system according to claim 1, wherein in the step 4), the filtered solution is continuously added with sulfuric acid with the concentration of 8-12 wt% to adjust the pH value to 9-10, the filter residue obtained by filtering is silicic acid, and the chemical reaction formula is as follows:
Na2SiO3+H2SO4＝H2SiO3+Na2SO4+H2O。
4. the process method for treating and utilizing the catalyst for preparing sulfuric acid from waste vanadium-silicon series according to claim 1, wherein in the step 6), Ca2+ is added in the vanadium precipitation process for vanadium precipitation treatment to form a calcium vanadate product.
5. The process method for treating and utilizing the catalyst for preparing sulfuric acid from waste vanadium-silicon series according to claim 1, wherein the pH value of the CaCl2 added in the step 6) is adjusted to 10.8-11.
6. The process method for treating and utilizing the catalyst used in the preparation of sulfuric acid from waste vanadium-silicon series according to claim 1, wherein the added Ca (OH)2 in the step 6) is adjusted to have a pH value of 7.8-9.3.
7. The process method for treating and utilizing the catalyst for preparing sulfuric acid from waste vanadium-silicon series according to claim 1, wherein the pH value of CaO added in the step 6) is adjusted to 5.1-6.1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491419A (en) * | 2011-12-05 | 2012-06-13 | 合肥工业大学 | Method for comprehensively recycling waste vanadium catalyst |
| CN103789550A (en) * | 2014-01-26 | 2014-05-14 | 郝喜才 | Method for recovering vanadium, potassium and silicon from waste vanadium catalyst |
| CN106622399A (en) * | 2016-12-16 | 2017-05-10 | 华北电力大学 | Recycling method of abandoned SCR (Selective Catalytic Reduction) denitration catalyst |
| CN107177737A (en) * | 2017-06-06 | 2017-09-19 | 开封大学 | Spent vanadium catalyst comprehensive reutilization method |
| CN111302397A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院城市环境研究所 | Method and device for recovering waste denitration catalyst |
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- 2020-08-03 CN CN202010767395.3A patent/CN111876604A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491419A (en) * | 2011-12-05 | 2012-06-13 | 合肥工业大学 | Method for comprehensively recycling waste vanadium catalyst |
| CN103789550A (en) * | 2014-01-26 | 2014-05-14 | 郝喜才 | Method for recovering vanadium, potassium and silicon from waste vanadium catalyst |
| CN106622399A (en) * | 2016-12-16 | 2017-05-10 | 华北电力大学 | Recycling method of abandoned SCR (Selective Catalytic Reduction) denitration catalyst |
| CN107177737A (en) * | 2017-06-06 | 2017-09-19 | 开封大学 | Spent vanadium catalyst comprehensive reutilization method |
| CN111302397A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院城市环境研究所 | Method and device for recovering waste denitration catalyst |
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Application publication date: 20201103 |