CN111068732A - Hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment - Google Patents
Hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment Download PDFInfo
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- CN111068732A CN111068732A CN201911330438.5A CN201911330438A CN111068732A CN 111068732 A CN111068732 A CN 111068732A CN 201911330438 A CN201911330438 A CN 201911330438A CN 111068732 A CN111068732 A CN 111068732A
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- hydrogen peroxide
- decomposition catalyst
- sulfuric acid
- waste acid
- peroxide decomposition
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000002699 waste material Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- 238000010306 acid treatment Methods 0.000 title abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 28
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 25
- 239000012629 purifying agent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 17
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052802 copper Chemical class 0.000 description 2
- 239000010949 copper Chemical class 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
Abstract
The invention discloses a hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment. The catalyst is prepared by the following method: mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out, drying, and roasting at 400-460 ℃ for 2-4 h. The carbon nitride catalyst structure disclosed by the invention has a cavity surrounded by pyridine type nitrogen-containing groups, has strong metal complexing ability, can change the valence band structure and the catalytic performance by introducing metal elements of manganese and iron, is stable in structure and performance, has strong acid and alkali resistance, and can reduce the content of hydrogen peroxide in waste acid to be less than 0.1%. The invention also provides a treatment method of the semiconductor waste acid, and the treated waste sulfuric acid solution can be used for preparing an aluminum sulfate water purifying agent to obtain the aluminum sulfate water purifying agentThe acidity of the obtained aluminum sulfate water purifying agent is below 0.5 percent, and Al is used2O3The calculated aluminum content is more than 6.5 percent, which meets the relevant standard of aluminum sulfate water purifying agent.
Description
Technical Field
The invention relates to the technical field of waste acid treatment, in particular to a hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment.
Background
In recent years, with the rapid development of the information industry, the semiconductor industry has come to a high-speed development period, and meanwhile, as global semiconductor manufacturers move the production capacity into China intensively, the semiconductor industry comes to new opportunities and challenges. With the smaller and smaller size of the semiconductor device and the higher integration degree, the influence of trace impurities in the semiconductor device on the semiconductor device is increased, and therefore, the amount of SPM waste acid generated by the semiconductor cleaning process is increased rapidly. The SPM waste acid contains 40-85% of sulfuric acid and 3-10% of hydrogen peroxide, and the residual hydrogen peroxide in the used waste acid is unfavorable for transportation, safe storage, recycling and reutilization in other production processes. If the sulfuric acid in the waste acid needs to be recycled, the peroxide must be decomposed and removed.
The industry currently uses the addition of metal ion catalysts directly to the spent acid, for example, water soluble salts of iron or copper may be added to the waste water stream under acidic conditions, whereby the decomposition of hydrogen peroxide occurs. However, the added copper or iron salts need to be subsequently removed from the wastewater stream, resulting in additional operating costs. And metal impurities are introduced, so that the catalyst cannot be recycled, and the cost control is not ideal. Another method for removing hydrogen peroxide is to use a reducing agent such as sodium bisulfite or the like, but it releases a large amount of gaseous sulfur dioxide, causing environmental pollution, and requires the use of a significant amount of a reducing agent such as sodium bisulfite, resulting in an increase in running costs. There are also the use of activated carbon for the removal of hydrogen peroxide from aqueous solutions, the use of activated carbon alone for the decomposition of hydrogen peroxide in aqueous solutions, catalytic activity, etc. And because various impurities exist in the acidic wastewater, the activated carbon is easy to poison, the catalytic activity of the activated carbon is further reduced, and the requirement on the treated waste acid raw material is higher. In addition, the activated carbon itself can be denatured under the strongly acidic conditions of hydrogen peroxide, additionally reducing the lifetime of the catalyst. The conventional photocatalytic decomposition of hydrogen peroxide is directly used, so that the time consumption is huge and the processing capacity is low.
CN108554442A discloses a new ferro-manganese two-component catalyst and a catalytic process for hydrogen peroxide, which prepares a molecular sieve loaded ferro-manganese hydrogen peroxide catalyst, but on one hand, the catalyst treats the hydrogen peroxide in a conventional hydrogen peroxide solution instead of complex SPM waste acid containing sulfuric acid and other components, and on the other hand, the catalyst only gives a relevant decomposition rate in the aspect of treatment effect, and the final treatment effect is not known,
disclosure of Invention
The invention aims to solve the technical problems of low decomposition and catalysis treatment capability and high treatment cost of hydrogen peroxide in the conventional SPM waste acid, and provides a hydrogen peroxide decomposition catalyst.
Another object of the present invention is to provide a use of a hydrogen peroxide decomposition catalyst for decomposing hydrogen peroxide in semiconductor waste acid.
The invention also aims to provide a method for treating the semiconductor waste acid.
The invention also aims to provide a preparation method of the aluminum sulfate water purifying agent.
The above purpose of the invention is realized by the following technical scheme:
a hydrogen peroxide decomposition catalyst prepared by the following method: mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out, drying, roasting and curing at 400-460 ℃ for 2-4 h to obtain the hydrogen peroxide decomposition catalyst.
According to the invention, the graphite-phase carbon nitride is modified by using an ethanol solution of manganese nitrate and ferric nitrate, metal active ions are solidified on the graphite-phase carbon nitride through complexation, so that the catalyst can be repeatedly utilized, and the decomposition of hydrogen peroxide promoted by the iron and manganese ions is caused by the generation of highly active radicals. The specific mechanism is as follows:
H2O2+Mn+—HO·+OH-+M(n+1)+
H2O2+HO·—HOO·+H2O
HOO·+M(n+1)+—O2+H++Mn+wherein M is a metal ion.
Wherein graphite phase carbon nitride g-C3N4The effect of dipping in the ethanol solution of manganese nitrate and ferric nitrate is as follows: the ethanol is easier to be prepared due to smaller surface tensionAnd (4) infiltration on the carrier.
The further roasting treatment is to remove volatile components in the catalyst, improve the mechanical strength of the catalyst and enable active components to be better solidified on the surface of the carrier.
The carbon nitride catalyst structure of the invention has a cavity surrounded by pyridine type nitrogen-containing groups, has strong metal complexing ability and has the metal complexing ability in g-C3N4The introduction of metal elements can change the valence band structure and the catalytic performance, and the structure and the performance are stable, and the catalyst has strong acid and alkali resistance, so the catalyst shows strong superiority in the process of catalytically decomposing hydrogen peroxide in semiconductor waste acid.
The dipping time is preferably 12-16 h, insufficient dipping can be caused by too short dipping time, and the catalyst preparation period can be prolonged by too long dipping time.
Preferably, the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 1-5: 1, and the concentration of ethanol is 95%.
For example, the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and iron nitrate is 2:1 or
The molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 5: 1;
or the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 3: 1.
More preferably, the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and iron nitrate is 5: 1.
The main reasons for controlling the molar ratio of manganese to iron are: the manganese has higher catalytic activity but higher market price, so the manganese and the manganese are used according to a certain proportion, and the balance point of catalytic effect and economic cost is sought.
Preferably, the graphite phase carbon nitride g-C3N4The preparation method comprises the following steps: heating melamine or urea to 500-550 ℃ under the protection of inert gas, calcining, cooling, and grinding to obtain graphite-phase carbon nitride g-C3N4。
Preferably, the temperature rise rate of the temperature rise is 5-10 ℃/min, and the calcination time is 4-6 h. Catalyst carrier preparation influenced by too slow temperature rise rateEfficiency, the precursor is put into the reactor when the temperature is too fast or high, the material can be rapidly decomposed, a large amount of gas is generated, and the influence on the graphite phase carbon nitride g-C3N4The yield of (A) was found.
Preferably, the graphite phase carbon nitride g-C3N4Has a particle size of 200 to 400 mesh and a specific surface area of 8 to 12m2/g。
The application of the hydrogen peroxide decomposition catalyst in decomposing hydrogen peroxide in semiconductor waste acid is also within the protection scope of the invention.
The invention also discloses a treatment method of the semiconductor waste acid, which comprises the following steps: adding the hydrogen peroxide decomposition catalyst into semiconductor waste acid, heating to 60-100 ℃, and reacting for 0.5-2 h to prepare the waste sulfuric acid solution from which hydrogen peroxide is removed.
The temperature is increased to 60-100 ℃, which is beneficial to the catalyst to obtain higher activation energy and improves the catalytic decomposition efficiency.
Wherein, the hydrogen peroxide decomposition catalyst of the present invention can be recycled after the reaction is completed. The specific recovery method comprises the following steps:
the filtered catalyst is washed by clean water, dried and recycled.
Preferably, the mass concentration of sulfuric acid in the semiconductor waste acid is 40-65%, and the mass concentration of hydrogen peroxide is 1-4%.
Preferably, the mass ratio of the semiconductor waste acid to the hydrogen peroxide decomposition catalyst is 20-100: 1 according to the content of hydrogen peroxide in the semiconductor waste acid.
For example, the mass ratio of the semiconductor waste acid to the hydrogen peroxide decomposition catalyst is 20: 1; or
The mass ratio of the semiconductor waste acid to the hydrogen peroxide decomposition catalyst is 40: 1.
More preferably, the mass ratio of the semiconductor waste acid to the hydrogen peroxide decomposition catalyst is 20: 1.
The invention also discloses a preparation method of the aluminum sulfate water purifying agent, which comprises the following steps:
s1, determining the content of hydrogen peroxide in the waste sulfuric acid solution, adding a potassium permanganate solution to react to remove residual hydrogen peroxide to obtain a pretreated waste sulfuric acid solution;
s2, measuring sulfuric acid in the pretreated waste sulfuric acid solution in the S1, adding soluble aluminum hydroxide, stirring for dissolving, controlling the acidity of the product to be below 0.5%, and adding Al2O3The calculated aluminum content is more than 6.5 percent, and the aluminum sulfate water purifying agent is prepared.
Wherein the adding amount of potassium permanganate in the S1 is 2 times of the mass content of the hydrogen peroxide in order to sufficiently remove the residual hydrogen peroxide.
And the content of hydrogen peroxide in the waste sulfuric acid solution in the S1 is determined by a potassium permanganate standard solution titration method.
Wherein the stirring and dissolving in the S2 are carried out under the heating condition, the heating temperature is 80-120 ℃, so that the soluble aluminum can be completely dissolved.
Compared with the prior art, the invention has the beneficial effects that:
the carbon nitride catalyst structure of the invention has a cavity surrounded by pyridine type nitrogen-containing groups, has strong metal complexing ability, and has carbon nitride g-C in graphite phase3N4The introduction of metal elements of manganese and iron can change the valence band structure and the catalytic performance of the catalyst, the catalyst has stable structure and performance and stronger acid and alkali resistance, and has strong superiority in the process of catalytically decomposing hydrogen peroxide in semiconductor waste acid, and the hydrogen peroxide content in the treated waste acid is less than 0.1 percent.
The invention also provides a method for treating the semiconductor waste acid, the treated waste sulfuric acid solution can be used for preparing the aluminum sulfate water purifying agent, the acidity of the prepared aluminum sulfate water purifying agent is below 0.5 percent, and Al is used2O3The calculated aluminum content is more than 6.5 percent, which meets the relevant standard of aluminum sulfate water purifying agent.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Wherein the content of the hydrogen peroxide in the waste sulfuric acid solution is determined by a potassium permanganate standard solution titration method.
The acidity of the waste sulfuric acid solution is determined by an acid-base titration method.
The aluminum content of the aluminum sulfate water purifying agent is determined by a back titration method of a zinc chloride standard titration solution.
Example 1
A hydrogen peroxide decomposition catalyst prepared by the following method:
30g of melamine is put into a crucible, the temperature is programmed to 550 ℃ at the speed of 5 ℃/h under the protection of nitrogen, the calcination is carried out for 6h, and the graphite-phase carbon nitride g-C is prepared by cooling and grinding3N4；
Mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out and drying, and roasting at 460 ℃ for 4h to obtain the hydrogen peroxide decomposition catalyst, wherein the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 2:1, and the concentration of ethanol is 95%.
Wherein the graphite phase carbon nitride g-C3N4Has a particle size of 200 mesh and a specific surface area of 10m2/g。
A treatment method of semiconductor waste acid comprises the following steps: 200g of waste acid is taken, the content of hydrogen peroxide is 3.73 percent, and the acidity is H2SO4) At 52%, 5g of the above hydrogen peroxide decomposition catalyst was added, the temperature was raised to 60 ℃ to react for 1 hour without substantially generating bubbles, and a waste sulfuric acid solution from which hydrogen peroxide was removed was prepared.
The hydrogen peroxide content of the waste sulfuric acid solution from which hydrogen peroxide was removed was measured to be 0.1%, and the removal rate was 97%.
Example 2
A preparation method of an aluminum sulfate water purifying agent comprises the following steps:
s1, adding 0.2g of potassium permanganate into the waste sulfuric acid solution obtained in the step 1, removing hydrogen peroxide, stirring for reacting fully, and removing residual hydrogen peroxide to obtain a pretreated waste sulfuric acid solution;
s2, measuring sulfuric acid in the pretreated waste sulfuric acid solution in the step S1, adding 60g of soluble aluminum hydroxide and 200g of water, heating to 95 ℃, and stirring for dissolving to prepare the aluminum sulfate water purifying agent.
The measured acidity of the aluminum sulfate water purifying agent is 0.48 percent by using Al2O3The calculated aluminum content is 7.23 percent, and the product is a qualified aluminum sulfate water purifying agent product.
Example 3
A hydrogen peroxide decomposition catalyst prepared by the following method:
30g of melamine is put into a crucible, the temperature is programmed to 550 ℃ at the speed of 10 ℃/h under the protection of nitrogen, the calcination is carried out for 4h, and the graphite-phase carbon nitride g-C is prepared by cooling and grinding3N4；
Mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out and drying, and roasting at 460 ℃ for 4 hours to obtain the hydrogen peroxide decomposition catalyst, wherein the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 5:1, and the concentration of ethanol is 95%.
Wherein the graphite phase carbon nitride g-C3N4Has a particle size of 400 mesh and a specific surface area of 12m2/g。
A treatment method of semiconductor waste acid comprises the following steps: 200g of waste acid is taken, the content of hydrogen peroxide is 2.68 percent, and the acidity is H2SO4) At 48%, adding 10g of the above hydrogen peroxide decomposition catalyst, heating to 100 ℃, reacting for 0.5h without generating bubbles, and preparing the waste sulfuric acid solution without hydrogen peroxide.
The hydrogen peroxide content of the waste sulfuric acid solution from which hydrogen peroxide was removed was measured to be 0.05%, and the removal rate was 98%.
Example 4
A preparation method of an aluminum sulfate water purifying agent comprises the following steps:
s1, adding 0.1g of potassium permanganate into the waste sulfuric acid solution obtained in the step 3, stirring and reacting fully, and removing residual hydrogen peroxide to obtain a pretreated waste sulfuric acid solution;
s2, measuring sulfuric acid in the pretreated waste sulfuric acid solution in the step S1, adding 50g of soluble aluminum hydroxide and 200g of water, heating to 100 ℃, and stirring for dissolving to prepare the aluminum sulfate water purifying agent.
The measured acidity of the aluminum sulfate water purifying agent is 0.09 percent by using Al2O3The calculated aluminum content is 7.62 percent, and the product is a qualified aluminum sulfate water purifying agent product.
Example 5
A hydrogen peroxide decomposition catalyst prepared by the following method:
30g of melamine is put into a crucible, the temperature is programmed to 550 ℃ at the speed of 10 ℃/h under the protection of nitrogen, the calcination is carried out for 5h, and the graphite-phase carbon nitride g-C is prepared by cooling and grinding3N4；
Mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out and drying, and roasting at 460 ℃ for 4 hours to obtain the hydrogen peroxide decomposition catalyst, wherein the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and ferric nitrate is 3:1, and the concentration of ethanol is 95%.
Wherein the graphite phase carbon nitride g-C3N4Has a particle size of 200 meshes and a specific surface area of 8m2/g。
A treatment method of semiconductor waste acid comprises the following steps: 200g of waste acid is taken, the content of hydrogen peroxide is 1.26 percent, and the acidity (by H)2SO4) 55 percent of the catalyst is added with 5g of the hydrogen peroxide decomposition catalyst, the temperature is raised to 60 ℃, basically no bubbles are generated after the reaction is carried out for 1 hour, and the waste sulfuric acid solution with the hydrogen peroxide removed is prepared.
The hydrogen peroxide content of the spent sulfuric acid solution from which hydrogen peroxide was removed was measured to be 0.08%, and the removal rate was 93%.
Example 6
A preparation method of an aluminum sulfate water purifying agent comprises the following steps:
s1, adding 0.16g of potassium permanganate into the waste sulfuric acid solution obtained in the step 5, stirring and reacting fully, and removing residual hydrogen peroxide to obtain a pretreated waste sulfuric acid solution;
s2, measuring sulfuric acid in the pretreated waste sulfuric acid solution in the step S1, adding 62g of soluble aluminum hydroxide and 240g of water, heating to 105 ℃, and stirring to dissolve to prepare the aluminum sulfate water purifying agent.
The measured acidity of the aluminum sulfate water purifying agent is 0.45 percent by using Al2O3The calculated aluminum content is 7.38 percent, and the product is a qualified aluminum sulfate water purifying agent product.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A hydrogen peroxide decomposition catalyst, characterized by being prepared by the following method: mixing graphite phase carbon nitride g-C3N4Soaking in an ethanol solution of manganese nitrate and ferric nitrate, taking out, drying, roasting and curing at 400-460 ℃ for 2-4 h to obtain the hydrogen peroxide decomposition catalyst.
2. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the molar ratio of manganese to iron in the ethanol solution of manganese nitrate and iron nitrate is 1-5: 1, and the concentration of ethanol is 95%.
3. The hydrogen peroxide decomposition catalyst of claim 1 wherein the graphite phase carbon nitride g-C3N4The preparation method comprises the following steps: heating melamine or urea to 500-550 ℃ under the protection of inert gas, calcining, cooling and grinding to obtain graphite-phase carbon nitride g-C with a certain specific surface area3N4。
4. The catalyst for decomposition of hydrogen peroxide according to claim 3, wherein the temperature rise rate is 5 to 10 ℃/min and the calcination time is 4 to 6 hours.
5. As claimed in claim 1The hydrogen peroxide decomposition catalyst according to claim 3 or 4, wherein the graphite-phase carbon nitride g-C3N4Has a particle size of 200 to 400 mesh and a specific surface area of 8 to 12m2/g。
6. Use of the hydrogen peroxide decomposition catalyst according to any one of claims 1 to 4 for decomposing hydrogen peroxide in semiconductor waste acid.
7. A method for treating semiconductor waste acid is characterized by comprising the following steps: adding the hydrogen peroxide decomposition catalyst according to any one of claims 1 to 4 into semiconductor waste acid, heating to 60 to 100 ℃, and reacting for 0.5 to 2 hours to prepare the waste sulfuric acid solution without hydrogen peroxide.
8. The method for treating semiconductor waste acid as claimed in claim 7, wherein the mass concentration of sulfuric acid in the semiconductor waste acid is 40-65%, and the mass concentration of hydrogen peroxide is 1-4%.
9. The treatment method of semiconductor waste acid as claimed in claim 8, wherein the mass ratio of the semiconductor waste acid to the hydrogen peroxide decomposition catalyst is 20-100: 1.
10. The preparation method of the aluminum sulfate water purifying agent is characterized by comprising the following steps:
s1, measuring the content of hydrogen peroxide in the waste sulfuric acid solution in claim 7, and adding a potassium permanganate solution to react to remove residual hydrogen peroxide to obtain a pretreated waste sulfuric acid solution;
s2, measuring sulfuric acid in the pretreated waste sulfuric acid solution in the S1, adding soluble aluminum hydroxide, stirring for dissolving, controlling the acidity of the product to be below 0.5%, and adding Al2O3The calculated aluminum content is more than 6.5 percent, and the aluminum sulfate water purifying agent is prepared.
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| CN114105106A (en) * | 2021-11-09 | 2022-03-01 | 上海天汉环境资源有限公司 | Method for removing hydrogen peroxide in waste sulfuric acid |
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