CN116571209A - Titanium-based hydrogen peroxide solution purification adsorbent and hydrogen peroxide purification method - Google Patents
Titanium-based hydrogen peroxide solution purification adsorbent and hydrogen peroxide purification method Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003463 adsorbent Substances 0.000 title claims abstract description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000010936 titanium Substances 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000746 purification Methods 0.000 title abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 244000060011 Cocos nucifera Species 0.000 claims description 7
- 238000005202 decontamination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 4
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims description 3
- BNVBVPNCFXAQEJ-UHFFFAOYSA-J [Ti+4].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Ti+4].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O BNVBVPNCFXAQEJ-UHFFFAOYSA-J 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- YRWWCNGKZLMTPH-UHFFFAOYSA-J prop-2-enoate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C YRWWCNGKZLMTPH-UHFFFAOYSA-J 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000003588 decontaminative effect Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 35
- 150000005837 radical ions Chemical class 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 150000005838 radical anions Chemical class 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- -1 organic matters Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000005839 radical cations Chemical class 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application discloses a titanium-based hydrogen peroxide solution purification adsorbent and a hydrogen peroxide purification method, wherein the titanium-based hydrogen peroxide solution purification adsorbent comprises active carbon and nano titanium oxide loaded in pores of the active carbon, and the mass ratio of the nano titanium oxide to the active carbon is (1-30): 100. according to the titanium-based hydrogen peroxide solution purification adsorbent, titanium oxide is compounded on activated carbon with larger specific surface area, the dispersibility of the titanium oxide is enhanced, the adsorption sites of the titanium oxide are effectively utilized, and meanwhile, the active carbon after the titanium oxide is compounded has the advantages that the TOC adsorption effect is improved, the adsorption performance is enhanced by the synergistic effect between the titanium oxide and the active carbon, and the adsorbent has excellent acid radical ion and TOC adsorption effects.
Description
Technical Field
The application belongs to the technical field of adsorption materials, and particularly relates to a titanium-based hydrogen peroxide solution purification adsorbent, and a preparation method and application thereof.
Background
Ultrapure hydrogen peroxide acts as a cleaning agent and an etchant in the production process of electronic integrated circuits. Ultrapure hydrogen peroxide is typically prepared from technical grade hydrogen peroxide. Currently, the predominant process for producing technical grade hydrogen peroxide is the anthraquinone process. The method mainly comprises three steps of hydrogenation, oxidation and extraction, and is limited by a process method, and the produced hydrogen peroxide has more impurity types, such as: organic matter, acid radical anions, metal cations, and the like. To obtain electronic grade hydrogen peroxide, post-treatment of technical grade hydrogen peroxide is required to remove the relevant impurities.
Currently, the purification and purification methods of industrial-grade hydrogen peroxide mainly comprise a rectification method, a membrane separation method, an adsorption method and ion exchange. The rectification method has the advantages of harsh operating conditions, high energy consumption and purification and concentration pretreatment. The membrane separation method has a good removal effect on metal ions only, and the application of the membrane separation method is limited due to the poor oxidation resistance of the organic membrane. The adsorption method adopts activated carbon adsorption, has good removal effect only on TOC, and has poor removal effect on metal cations and acid radical cations. The ion exchange method is mature in process and is widely applied, but hydrogen peroxide is inevitably decomposed when anion exchange resin is used for removing acid radical ions and various resins are regenerated, and the TOC removal effect of macroporous adsorption resin is limited.
Thus, there is a need to explore new purification methods and materials suitable for hydrogen peroxide systems.
Disclosure of Invention
The application aims to provide a titanium-based hydrogen peroxide solution purifying adsorbent method and a hydrogen peroxide purifying method, which are used for solving the technical problems that the industrial-grade hydrogen peroxide purifying method in the prior art has harsh operation conditions and high energy consumption and cannot remove impurities such as organic matters, acid radical anions, metal cations and the like at the same time.
In order to achieve the above purpose, the application adopts a technical scheme that:
a titanium-based hydrogen peroxide solution purification adsorbent is provided, comprising activated carbon and nano titanium oxide loaded in the pores of the activated carbon.
In one or more embodiments, the mass ratio of the nano titanium oxide to the activated carbon is (1 to 30): 100.
in one or more embodiments, the activated carbon comprises one or more combinations of coconut shell activated carbon, drug dehydrated activated carbon, purified water activated carbon, bio-based activated carbon, coal-based activated carbon.
In order to achieve the above purpose, another technical scheme adopted by the application is as follows:
there is provided a method for producing the titanium-based hydrogen peroxide solution purification adsorbent according to any one of the above embodiments, comprising:
dispersing active carbon in deionized water to obtain suspension;
adding titanium salt into the suspension, and carrying out mixed reaction under a hydrothermal condition to obtain a reaction solution;
and filtering, washing and drying the reaction liquid in sequence to obtain the titanium-based hydrogen peroxide solution purifying adsorbent.
In one or more embodiments, the titanium salt comprises one or more of titanium chloride, titanium sulfate, titanium acetate, titanium n-propoxide, titanium silicate, titanium fluoride, titanium propionate, titanium acrylate.
In one or more embodiments, the hydrothermal conditions are 150 to 180 ℃.
In order to achieve the above object, another technical scheme adopted by the present application is as follows:
there is provided a hydrogen peroxide decontamination method comprising: the titanium-based hydrogen peroxide solution purifying adsorbent according to any one of the embodiments described above is added to a hydrogen peroxide solution to adsorb multiple impurities.
In one or more embodiments, the multiple impurities include organic impurities, metal cations, and acid anions.
In one or more embodiments, the concentration of the titanium-based hydrogen peroxide solution scavenger adsorbent in the hydrogen peroxide solution is in the range of 0.1 to 5g/L.
In one or more embodiments, the adsorption time of the titanium-based hydrogen peroxide solution purifying adsorbent in the hydrogen peroxide solution is 0.5 to 4 hours, and the adsorption temperature is 25 to 35 DEG C
Compared with the prior art, the application has the beneficial effects that:
according to the titanium-based hydrogen peroxide solution purification adsorbent, titanium oxide is compounded on activated carbon with larger specific surface area, the dispersibility of the titanium oxide is enhanced, the adsorption sites of the titanium oxide are effectively utilized, and meanwhile, the active carbon after the titanium oxide is compounded has the advantages that the TOC adsorption effect is improved, the adsorption performance is enhanced by the synergistic effect between the titanium oxide and the active carbon, and the adsorbent has excellent acid radical ion and TOC adsorption effects;
the titanium-based hydrogen peroxide solution purifying adsorbent has good adsorption effect on acid radical anions and organic impurities, wherein the TOC removal rate reaches 96.3%, the phosphate radical anion removal rate reaches 47.3%, and the sulfate radical anion removal rate reaches 29.82%;
the titanium-based hydrogen peroxide solution purifying adsorbent has good adsorption effect on organic impurities, acid radical anions and metal ions in the hydrogen peroxide solution, and the decomposition rate of hydrogen peroxide before and after adsorption is not more than 0.80%.
Drawings
FIG. 1 is a physical isothermal adsorption isotherm of example 1 and comparative example 2 of the present application;
fig. 2 is a pore size distribution curve of inventive example 1 and comparative example 2.
Detailed Description
The present application will be described in detail below with reference to the embodiments shown in the drawings. The embodiments are not intended to limit the application, but structural, methodological, or functional modifications of the application from those skilled in the art are included within the scope of the application.
Limited by the process, the currently produced industrial grade hydrogen peroxide has a large variety of impurities, such as: organic matter, acid radical anions, metal cations, and the like. In order to obtain ultra-pure electronic grade hydrogen peroxide, it is necessary to remove impurities from technical grade hydrogen peroxide.
Currently, the purification and purification methods of industrial-grade hydrogen peroxide mainly comprise a rectification method, a membrane separation method, an adsorption method and ion exchange. The rectification method has the advantages of harsh operating conditions, high energy consumption and purification and concentration pretreatment. The membrane separation method has a good removal effect on metal ions only, and the application of the membrane separation method is limited due to the poor oxidation resistance of the organic membrane. The adsorption method adopts activated carbon adsorption, has good removal effect only on TOC, and has poor removal effect on metal cations and acid radical cations. The ion exchange method is mature in process and is widely applied, but hydrogen peroxide is inevitably decomposed when anion exchange resin is used for removing acid radical ions and various resins are regenerated, and the TOC removal effect of macroporous adsorption resin is limited.
In order to solve various defects existing in the existing industrial-grade hydrogen peroxide purification and purification method, the applicant develops a novel titanium-based hydrogen peroxide solution purification adsorbent which can synchronously adsorb organic matters, acid radical anions and metal cations in the industrial-grade hydrogen peroxide, so that the purification and purification production problems of the industrial-grade hydrogen peroxide are effectively solved, the production efficiency of the electronic-grade hydrogen peroxide is improved, and the problem of hydrogen peroxide decomposition is avoided.
Specifically, the titanium-based hydrogen peroxide solution purification adsorbent comprises activated carbon and nano titanium oxide loaded in the pores of the activated carbon.
In one application scenario, the mass ratio of the nano titanium oxide to the activated carbon may be (1-30): 100.
in one application scenario, the activated carbon may be one or a combination of more of coconut shell activated carbon, drug dehydrated activated carbon, purified water activated carbon, other bio-based activated carbon, coal-based activated carbon.
The application also provides a preparation method of the titanium-based hydrogen peroxide solution purification adsorbent, which comprises the following steps:
s100, dispersing the activated carbon in deionized water to obtain a suspension.
And S200, adding titanium salt into the suspension, and carrying out mixed reaction under a hydrothermal condition to obtain a reaction solution.
Wherein the titanium salt can be one or more of titanium chloride, titanium sulfate, titanium acetate, titanium n-propoxide, titanium silicate, titanium fluoride, titanium propionate and titanium acrylate
The hydrothermal reaction may be
And S300, sequentially filtering, washing and drying the reaction solution to obtain the titanium-based hydrogen peroxide solution purification adsorbent.
It is to be understood that this embodiment only exemplifies a method of preparing the titanium-based hydrogen peroxide solution purification adsorbent by a hydrothermal method, and in other embodiments, the titanium-based hydrogen peroxide solution purification adsorbent of the above embodiment may be prepared by a solvothermal method, a sol-gel method, a precipitation method, or the like.
The technical effects of the technical scheme of the present application are further described below in conjunction with specific embodiments.
Example 1:
the titanium-based hydrogen peroxide solution purifying adsorbent comprises medicine dehydration activated carbon and nano titanium oxide loaded in the pores of the medicine dehydration activated carbon, wherein the mass ratio of the nano titanium oxide to the activated carbon is 3:10.
the titanium-based hydrogen peroxide solution purifying adsorbent is prepared by the following steps:
dispersing the medicine dehydrated activated carbon in deionized water to form suspension, adding titanium chloride, mixing and reacting under hydrothermal condition, filtering, washing and drying after the reaction is completed to obtain the titanium-based hydrogen peroxide solution purification adsorbent.
Example 2:
the titanium-based hydrogen peroxide solution purifying adsorbent comprises coconut shell activated carbon and nano titanium oxide loaded in the pores of the coconut shell activated carbon, wherein the mass ratio of the nano titanium oxide to the activated carbon is 1:10.
the titanium-based hydrogen peroxide solution purifying adsorbent is prepared by the following steps:
dispersing coconut shell activated carbon in deionized water to form suspension, adding titanium acetate, mixing and reacting under hydrothermal condition, filtering, washing and drying to obtain the titanium-based hydrogen peroxide solution purification adsorbent.
Example 3:
the titanium-based hydrogen peroxide solution purifying adsorbent comprises purified water activated carbon and nano titanium oxide loaded in the pores of the coconut shell activated carbon, wherein the mass ratio of the nano titanium oxide to the activated carbon is 1:100.
the titanium-based hydrogen peroxide solution purifying adsorbent is prepared by the following steps:
and (3) weighing purified water activated carbon, dispersing the purified water activated carbon in deionized water to form suspension, adding titanium chloride, mixing the suspension with the titanium chloride under a hydrothermal condition for reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the titanium-based hydrogen peroxide solution purification adsorbent.
Comparative example 1:
a commercial titanium oxide adsorbent (CAS: 13463-67-7) was used as comparative example 1.
Comparative example 2:
commercial activated carbon (purchased from Aba Ding Shiji Co., CAS: 7440-44-0) was taken as comparative example 2.
Effect example 1:
the adsorption amounts of nitrogen at different equilibrium pressures were measured for the adsorbents of example 1 and comparative example 2 by gas adsorption to give fig. 1, and fig. 1 is a physical isothermal adsorption isotherm of example 1 and comparative example 2 of the present application.
Meanwhile, pore size distribution curves of the adsorbents of example 1 and comparative example 2 were measured by a gas adsorption method to obtain fig. 2, and fig. 2 is a pore size distribution curve of the adsorbents of example 1 and comparative example 2 of the present application.
Referring to fig. 1 and 2, the titanium-based hydrogen peroxide solution purification adsorbent of example 1 has better adsorption performance than the activated carbon adsorbent, mainly because nano titanium oxide is loaded in the pores of the activated carbon, exposing more adsorption sites.
Effect example 2:
a simulated solution having a TOC content of 47.01ppm was prepared, 20mL of the simulated solution was placed in a round-bottom beaker, 20mg of the adsorbents of example 1 and comparative example 2 were respectively added to the round-bottom beaker, and the adsorbents were adsorbed for 2 hours under a water bath condition at 30℃to measure the TOC content in the adsorbed solution, thereby obtaining the data of the following table.
As can be seen from the above table, the activated carbon adsorbent of comparative example 2 has a certain adsorption effect on TOC, probably due to the higher specific surface area and developed pore structure of activated carbon and the better affinity ability for organic impurities.
The titanium-based hydrogen peroxide solution purification adsorbent of example 1 has more excellent TOC adsorption performance than activated carbon, and the TOC removal rate reaches 96.3%, and it has been unexpectedly found that the TOC adsorption effect of activated carbon after titanium oxide is compounded is improved, and the synergistic effect between titanium oxide and activated carbon enhances the adsorption performance, which makes the adsorbent have excellent TOC adsorption effect.
Effect example 3:
preparing 10.213ppm of phosphate radical and SO 4 2- The content of NO is 0.309ppm 3- A simulated solution at a level of 0.617 ppm.
20mL of the simulated solution was placed in a round-bottomed flask, 20mg of the adsorbents of example 2 and comparative example 1 were added, respectively, and the adsorbents were adsorbed for 2 hours under a water bath condition at 30℃to measure the ion content in the adsorbed solution, thereby obtaining the data of the following table.
As shown in the above table data, the titania adsorbent of comparative example 1 has a good adsorption effect on phosphate ions, but has little adsorption effect on sulfate and nitrate, even though the sulfate and nitrate content is increased, which may be related to the small amount of sulfate and nitrate residues on the surface of commercial nano-titania.
The titanium-based hydrogen peroxide solution purification adsorbent prepared in example 2 has a good adsorption effect on acid radical anions, wherein the removal rate of the phosphate radical anions reaches 47.3%, and the removal rate of the sulfate radical anions reaches 29.82%, mainly because the dispersibility of titanium oxide is enhanced after the titanium oxide is compounded with active carbon with a larger specific surface area, and adsorption sites of the titanium oxide are effectively utilized.
Effect example 4:
preparing phosphate content 13.625ppm and SO 4 2- At a level of 0.234ppm NO 3- A simulated solution at a level of 0.417 ppm.
Putting 20mL of the simulated solution into a round-bottom flask, respectively adding 20mg of the adsorbent of example 3, and adsorbing for 2 hours under the water bath condition of 30 ℃; then, the solution was filtered through a 0.25. Mu.l aqueous filter membrane, and the filtrate was placed in a clean round-bottom flask, 20mg of the adsorbent of example 3 was further added, and the solution was adsorbed for 2 hours in a water bath at 30℃to measure the ion content of the adsorbed solution, whereby the data shown in the following table were obtained.
As can be seen from the above table data, the phosphate in the pseudo solution was completely adsorbed after the two times of adsorption by the adsorbent of example 3, and the sulfate and nitrate contained in the pseudo solution were less likely to compete with the phosphate for adsorption, so that the change was small.
As compared with effect example 3, it is understood that the impurity removal efficiency can be effectively enhanced by increasing the amount of the adsorbent and the number of times of adsorption.
Effect example 5:
a simulated solution having a phosphate content of 11.250ppm and a TOC content of 25.52ppm was prepared, 40mg of the adsorbent of example 3 was put into a round bottom beaker, and adsorbed for 2 hours under a water bath condition of 30℃to measure the TOC content and the phosphate content in the adsorbed solution, thereby obtaining the data of the following table.
| Impurity species | Before adsorption (ppm) | After adsorption (ppm) | Removal rate (%) |
| PO 4 3- | 11.250 | 5.505 | 51.1 |
| TOC | 25.52 | 3.15 | 87.7 |
From the above table data, it can be seen that the titanium-based hydrogen peroxide solution purification adsorbent of example 3 is capable of efficiently adsorbing both acid radical anions and organic impurities in a solution containing TOC and acid radical anions.
Meanwhile, compared with effect example 2, in the solution containing both TOC and acid radical anions, the adsorption effect of the titanium-based hydrogen peroxide solution purification adsorbent on TOC is reduced, which may be related to the competing adsorption between the impurity components.
Effect example 6:
20mL of hydrogen peroxide solution was placed in a round-bottomed flask, 20mg of the adsorbent of example 1 was added, and the mixture was adsorbed for 2 hours in a water bath at 30℃to measure the phosphate content, TOC content and metal ion content of the solution before and after the adsorption, respectively, to obtain the data shown in the following table. Wherein the metal ions include potassium ion, sodium ion, calcium ion, magnesium ion, aluminum ion and iron ion.
As shown in the above table, the titanium-based hydrogen peroxide solution purification adsorbent of example 1 has a good adsorption effect on organic impurities, acid radical anions and metal ions, and the decomposition rate of hydrogen peroxide before and after adsorption is not more than 0.80%.
The TOC adsorption effect and the phosphate adsorption effect of the adsorbent in hydrogen peroxide were reduced as compared with effect example 2 and effect example 3, which may be related to competitive adsorption between impurities.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A titanium-based hydrogen peroxide solution purifying adsorbent is characterized by comprising activated carbon and nano titanium oxide loaded in the pores of the activated carbon.
2. The titanium-based hydrogen peroxide solution purifying adsorbent according to claim 1, wherein a mass ratio of the nano titanium oxide to the activated carbon is (1 to 30): 100.
3. the titanium-based hydrogen peroxide solution purifying adsorbent of claim 1, wherein the activated carbon comprises one or more of coconut activated carbon, drug dehydrated activated carbon, purified water activated carbon, bio-based activated carbon, coal-based activated carbon.
4. A method for producing the titanium-based hydrogen peroxide solution purifying adsorbent as claimed in any one of claims 1 to 3, comprising:
dispersing active carbon in deionized water to obtain suspension;
adding titanium salt into the suspension, and carrying out mixed reaction under a hydrothermal condition to obtain a reaction solution;
and filtering, washing and drying the reaction liquid in sequence to obtain the titanium-based hydrogen peroxide solution purifying adsorbent.
5. The method according to claim 4, wherein the titanium salt comprises one or more of titanium chloride, titanium sulfate, titanium acetate, titanium n-propoxide, titanium silicate, titanium fluoride, titanium propionate, and titanium acrylate.
6. The process according to claim 4, wherein the hydrothermal conditions are 150 to 180 ℃.
7. A method for purifying hydrogen peroxide, comprising: adding the titanium-based hydrogen peroxide solution purifying adsorbent according to any one of claims 1 to 3 to a hydrogen peroxide solution to adsorb multiple impurities.
8. The hydrogen peroxide decontamination method of claim 7, wherein said multiple impurities comprise organic impurities, metal cations, and acid anions.
9. The hydrogen peroxide decontamination method according to claim 7, wherein a concentration of said titanium-based hydrogen peroxide solution decontamination adsorbent in said hydrogen peroxide solution is between 0.1 and 5g/L.
10. The hydrogen peroxide decontamination method according to claim 7, wherein said titanium-based hydrogen peroxide solution decontamination adsorbent has an adsorption time of 0.5 to 4 hours and an adsorption temperature of 25 to 35 ℃.
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