CN113648971B - Preparation method of porous zirconium carbon adsorption material - Google Patents
Preparation method of porous zirconium carbon adsorption material Download PDFInfo
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- CN113648971B CN113648971B CN202111059099.9A CN202111059099A CN113648971B CN 113648971 B CN113648971 B CN 113648971B CN 202111059099 A CN202111059099 A CN 202111059099A CN 113648971 B CN113648971 B CN 113648971B
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- 239000000463 material Substances 0.000 title claims abstract 13
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 title claims abstract 11
- 238000001179 sorption measurement Methods 0.000 title claims abstract 11
- 238000002360 preparation method Methods 0.000 title claims abstract 4
- 238000003756 stirring Methods 0.000 claims abstract 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000008367 deionised water Substances 0.000 claims abstract 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract 5
- 229940116318 copper carbonate Drugs 0.000 claims abstract 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract 5
- 239000007769 metal material Substances 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims abstract 5
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims abstract 5
- 239000000126 substance Substances 0.000 claims abstract 5
- 239000011812 mixed powder Substances 0.000 claims abstract 4
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 claims abstract 4
- 239000011230 binding agent Substances 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000002184 metal Substances 0.000 claims abstract 3
- 238000000227 grinding Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000000465 moulding Methods 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 4
- 229940044175 cobalt sulfate Drugs 0.000 claims 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims 4
- 238000005303 weighing Methods 0.000 claims 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 4
- 229960001763 zinc sulfate Drugs 0.000 claims 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 3
- 239000001099 ammonium carbonate Substances 0.000 claims 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 1
- 239000011268 mixed slurry Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 abstract 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 150000003751 zinc Chemical class 0.000 abstract 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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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
- B01J20/06—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
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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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to preparation of an adsorption material, in particular to a preparation method of a porous zirconium carbon adsorption material; the method comprises the steps of carrying out metal impregnation self-deposition load modification on the hydrous zirconia, dissolving soluble zinc salt or copper salt, cobalt salt and alkaline substances by using deionized water, and generating a zirconium-based multi-metal adsorption material on the surface and in holes of the hydrous zirconia in a uniformly slow dropwise adding and stirring mode; then ammonia water is used for dissolving basic zinc carbonate, basic copper carbonate and ammonia sulfate, and the impregnated active carbon powder is prepared by impregnating and carrying the basic zinc carbonate, the basic copper carbonate and the ammonia sulfate on an active carbon powder carrier in a water bath heating mode; finally, mixing and grinding the impregnated activated carbon powder and the zirconium-based multi-element metal material, and bonding and molding the mixed powder by adopting a binder to obtain a porous zirconium carbon adsorption material; the porous zirconium carbon adsorption material has better protection capability on toxic and harmful gases with larger property differences, such as benzene, hydrocyanic acid, cyanogen chloride, sulfur dioxide, hydrogen sulfide, ammonia gas and the like.
Description
Technical Field
The invention relates to preparation of an adsorption material, in particular to a preparation method of a porous zirconium carbon adsorption material.
Background
The activated carbon has high specific surface area and abundant micropore content, so that the activated carbon is widely applied to adsorbing toxic and harmful gases in the environment, particularly has excellent adsorption capacity on benzene molecules, but has almost no adsorption capacity on typical military toxicants such as HCN/CNCl and toxic and harmful industrial gases such as sulfur dioxide, ammonia and the like. The activated carbon needs to be impregnated with a metal active component to improve its protection against polar small molecules or physically unadsorbed toxic gases (HCN/CNCl). However, the activated carbon after metal impregnation cannot have the capability of comprehensively and efficiently protecting the gas molecules with different properties such as ammonia gas, sulfur dioxide, cyanogen chloride and the like in a broad spectrum at the same time, for example, the patent application No. CN200610056702.7 discloses an impregnated activated carbon and a preparation method thereof, wherein the patent uses the activated carbon as a carrier to dissolve copper scraps to prepare a copper-containing active component, and simultaneously impregnates active components such as metal potassium and the like to prepare the impregnated activated carbon, which can be used for protecting sulfur dioxide, nitrogen dioxide, benzene, hydrogen sulfide gas, but the impregnated carbon does not relate to the protection effect on ammonia gas, hydrocyanic acid and cyanogen chloride; the patent application No. CN00128283.2 is a chromium-free impregnated activated carbon and a preparation method thereof, and the patent uses an ammonia water solution to dissolve basic copper carbonate, zinc carbonate, ammonium chloride, ammonium molybdate and silver nitrate to impregnate the activated carbon, so that the impregnated carbon can be used for protecting hydrocyanic acid, sulfur dioxide, chlorine, ammonia and benzene, and the impregnated carbon does not give the protection effect of cyanogen chloride, and does not mention the protection effect of hydrogen sulfide.
The hydrous zirconia is taken as a mesoporous material with rich hydroxyl functional groups and higher specific surface area, has natural excellent adsorption capacity to toxic and harmful acid gases such as sulfur dioxide, and has the protective capacity to sulfur dioxide, such as Gregory and the like, and the protective time to sulfur dioxide gas of 89min of 70Penetration capacity of 78 mg/g. (Gregory W.Peterson, christopher J.Karwacki, william B.Feaver. Zirconium Hydroxide as a Reactive Substrate for the Removal of Sulfur Dioxide [ J)].Industrial&Engineering Chemistry Research,2009,48 (4): 1694-1698). However, according to previous experiments, the hydrated zirconia has little protection capability on physical adsorption type gas benzene molecules due to the low specific surface area, and meanwhile, the hydrated zirconia has little protection capability on chemical adsorption catalytic type gas hydrocyanic acid, cyanogen chloride and other toxic agents due to low content of differential metal active sites. However, by virtue of the abundant mesoporous structure of the hydrous zirconia and the advantage that zirconium metal is extremely easy to interact with other metal active components, the hydrous zirconia is carried with metal to be expected to achieve better protective capability on hydrocyanic acid and cyanogen chloride, for example, the patent application number is as follows; after the zirconium hydroxide powder was subjected to sulfuric acid treatment by Glover, a penetration capacity of 3.9mol/kg was exhibited for ammonia gas, but the protective properties of sulfur dioxide, hydrocyanic acid, and cyanogen chloride were not given. (t.grant Glover,Gregory W.Peterson,/>Jared B.DeCoste,/>and Matthew A.Browe/>Adsorption of Ammonia by Sulfuric Acid Treated Zirconium Hydroxide[J]langmuir,2012,28,10478-10487). Meanwhile, by utilizing the advantages of the modified hydrous zirconia and the activated carbon material on gas protection, the novel adsorption material with good protection capability on toxic and harmful gases with large property difference is hopeful to be prepared.
Disclosure of Invention
The invention provides a preparation method of a porous zirconium carbon adsorption material, which aims to solve the technical problems that the existing adsorption material only has a protective effect on a certain specific toxic gas, does not have broad spectrum and does not have high-efficiency comprehensive protective capability, and the prepared Kong Gaotan adsorption material has high capacity and broad-spectrum protective performance, has better protective capability on toxic and harmful gases with larger property differences, such as benzene, hydrocyanic acid, cyanogen chloride, sulfur dioxide, hydrogen sulfide, ammonia gas and the like, has simple process and provides significant exploration for the large-scale research and development and production of a new generation of broad-spectrum protective material.
In order to solve the technical problems, the invention adopts the following technical scheme: firstly, a method for carrying out metal impregnation self-deposition load modification on hydrous zirconia is adopted, deionized water is used for dissolving soluble zinc salt or copper salt, cobalt salt and alkaline substances, and a zirconium-based multi-metal adsorption material is generated on the surface and in holes of the hydrous zirconia in a uniformly slow dropwise adding and stirring mode; then ammonia water is used for dissolving basic zinc carbonate, basic copper carbonate and ammonia sulfate, and the impregnated active carbon powder which has abundant micropore content and metal active components is prepared by impregnating and carrying the active carbon powder carrier in a water bath heating mode; finally, mixing and grinding the impregnated activated carbon powder and the zirconium-based multi-element metal material to enlarge the intermetallic thermal composite synergistic effect, and bonding and molding the mixed powder by adopting a bonding agent to obtain the porous zirconium-carbon adsorption material.
As the existing hydrous zirconia material contains rich hydroxyl functional groups, the hydrous zirconia material has excellent protection capability on sulfur dioxide and hydrogen chloride, has a certain adsorption effect on ammonia gas, has extremely poor dynamic protection capability, and simultaneously has no protection capability on toxic gases such as benzene molecules, hydrocyanic acid and the like; meanwhile, although the active carbon and the impregnated active carbon contain abundant micropores, the active carbon has no high-efficiency comprehensive protection capability for toxic agents with large property differences such as ammonia, sulfur dioxide, cyanogen chloride and the like.
The porous zirconium carbon adsorption material is prepared by adopting the self-deposition of the metal active component on the surface of the metal mesoporous material, utilizing the advantage that the metal mesoporous material is rich in functional groups and is very easy to cooperate and cooperate with metal, and combining the characteristic that the active carbon is rich in micropore property. The preparation method has better protection capability for typical physical adsorption type gas and chemical adsorption catalytic reaction type gas, lays a foundation for further development of a later-period broad-spectrum protection material, and has great research and development and production significance for the broad-spectrum protection field of military and civil toxicants.
The invention prepares a zirconium-based multielement metal material for efficiently protecting various gases such as hydrocyanic acid, cyanogen chloride and the like by carrying out metal impregnation, self-deposition and load modification on hydrous zirconia, mainly using zinc sulfate, cobalt sulfate and potassium hydroxide and utilizing the characteristics of exposed zirconium metal and larger pore diameter distribution and adopting the principle of interaction between active components, but is not limited to adding or replacing other metal components such as copper nitrate, ferric sulfate, ferric chloride and the like on the basis.
The porous zirconium-carbon adsorption material capable of protecting various different-property toxicants is finally prepared by utilizing the advantages of rich multi-metal active sites in the zirconium-based material and high specific surface area of the powder carbon, adopting a method of grinding the two powder materials and interacting with each other between metals to prepare a powder mixed material, and then carrying out binder forming on the powder material, but the porous zirconium-carbon adsorption material is not limited to the porous zirconium-carbon adsorption material, and zirconium-based powder and other powder with high specific surface area or other mixed modes except grinding can be used.
Further, the method specifically comprises the following steps:
step one, preparing a zirconium-based multi-element metal material:
a. weighing hydrated zirconia, adding deionized water, and stirring to obtain slurry;
b. weighing alkaline substances, adding deionized water, and stirring until the alkaline substances are dissolved;
c. slowly adding the solution in the step (b) into the solution in the step (a), regulating the pH of the whole slurry to 9-11, and stirring for 1-6 h;
d. weighing zinc sulfate and cobalt sulfate, adding deionized water, and stirring until the zinc sulfate and the cobalt sulfate are dissolved;
e. dropwise adding the solution in the step one d into the mixed slurry added in the step c at the speed of 1-6 drops/s, simultaneously adding the solution in the step b in an auxiliary way to ensure that the pH of the slurry is 9-11, and then stirring for 2-8 h;
f. filtering the slurry obtained in the step one, cleaning the slurry with deionized water for 3 times, and drying the slurry at 40-100 ℃ for 3-12 hours to obtain a zirconium-based multi-element metal material;
step two, preparing impregnated activated carbon powder with metal active components:
a. weighing basic copper carbonate, basic zinc carbonate, ammonium bicarbonate and ammonium sulfate, dissolving in an ammonia water solution, and stirring until the basic copper carbonate, the basic zinc carbonate, the ammonium bicarbonate and the ammonium sulfate are completely dissolved;
b. adding the solution obtained in the step two into activated carbon powder, uniformly stirring at room temperature, and then drying in an oven for 24 hours to obtain impregnated activated carbon powder;
step three, preparing a porous zirconium carbon adsorption material:
a. grinding and mixing the zirconium-based multielement metal material obtained in the first step with the impregnated activated carbon powder obtained in the second step for 5-60 min;
b. adding the mixed powder obtained in the step three a into Triethylenediamine (TEDA), sealing, and standing at 60 ℃ for 4 hours;
c. and d, bonding and molding the mixed powder obtained in the step b by adopting a bonding agent, and preparing the mixed powder into 0.6-1.2 mm particles for standby.
Preferably, in the step a, the mass ratio of the hydrous zirconia to the deionized water is 1:6; in the second step b, the mass ratio of the alkaline substance to the deionized water is 2-7:2-8; in the step one d, the mass ratio of the zinc sulfate to the cobalt sulfate to the deionized water is 10-200:1-60:300-800.
Preferably, in the step two a, the mass ratio of the basic copper carbonate to the basic zinc carbonate to the ammonium bicarbonate to the ammonium sulfate to the ammonia water is 2-40:0.01-10 g: 5-30: 1-40: 120; in the second step b, the mass ratio of the ammonia water to the activated carbon powder is 6:5.
Preferably, the ratio of the zirconium-based multi-component metal material to the impregnated activated carbon powder in the step three a is 3-6:1-6; and (c) adding ethylene diamine in the third step (b) in an amount which is 1-15% of the mass of the mixed powder obtained in the step (a).
Preferably, the stirring temperature in the first step is 25-40 ℃; the stirring temperature in the second step a is 30-65 ℃, and the drying temperature in the second step b is 140-200 ℃.
Further, the alkaline substance in the step one b is potassium hydroxide or sodium hydroxide.
As a further improvement of the technical scheme of the invention, the zinc sulfate in the step d is replaced by one or more of copper sulfate, copper nitrate, zinc chloride, ferric sulfate and ferric chloride, and the cobalt sulfate in the step d is replaced by cobalt chloride or cobalt nitrate.
Preferably, the binder in the step (c) is one of silica sol, tar, polyvinyl alcohol and hydroxymethyl fiber.
As a further improvement of the technical scheme of the invention, the metal salt in the step two a is replaced by one or more of tungsten, iron and molybdenum metal salts; the activated carbon powder in the step B is replaced by one or more of coal, wood and asphaltene porous materials with high specific surface area
Compared with the prior art, the invention has the following beneficial effects:
the hydrous zirconia material has rich functional groups, but has low specific surface area, contains only zirconium metal, has low content of differential metal active sites, almost has no adsorption capacity on benzene molecules, ammonia gas, hydrocyanic acid and cyanogen chloride molecules, prepares a zirconium-based multi-metal adsorption material capable of efficiently protecting hydrocyanic acid and cyanogen chloride gas by carrying out metal loading modification on the zirconium-based multi-metal adsorption material, and then combines the zirconium-based multi-metal adsorption material with the abundant micropore property of active carbon to prepare the high-capacity zirconium-carbon adsorbent capable of protecting various property differential toxicants by utilizing the abundant micropore property of active carbon, thereby providing beneficial exploration for large-scale research and development and use of a new generation of broad-spectrum protection material.
The porous zirconium carbon adsorbent prepared by the preparation method has better protection capability on physical adsorption type gas benzene molecules, acid gas sulfur dioxide, hydrogen sulfide, alkaline molecular ammonia gas, military chemical catalytic type toxic and harmful gases such as hydrocyanic acid, cyanogen chloride and the like with larger property difference, and the impregnating active carbon sold at present has almost no protection capability on ammonia gas.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
1) 200g of hydrous zirconia is weighed, 1200g of deionized water is added, and the mixture is stirred into slurry at 25 ℃;
2) Weighing 50g of potassium hydroxide, adding 50g of deionized water, and stirring until the potassium hydroxide is dissolved;
3) Slowly adding the solution obtained in the step 2) into the solution obtained in the step 1), adjusting the pH of the whole slurry to 9-11, and stirring for 3h at 25 ℃;
4) 80g of zinc sulfate and 20g of cobalt sulfate are weighed, 500g of deionized water is added, and stirring is carried out at 25 ℃ until the solution is dissolved;
5) Dropwise adding the solution of 4) into the mixed slurry added in 3) at a speed of 3 drops/s, simultaneously adding the solution of 2) in an auxiliary way, enabling the pH of the slurry to be 9-11, and then stirring for 3h at 25 ℃;
6) Filtering the slurry of the step 5), washing the filtered slurry with 2000g of deionized water for 3 times, and then drying the filtered slurry at 60 ℃ for 8 hours) to obtain a zirconium-based multi-element metal material;
7) Weighing 20g of basic copper carbonate, 2g of basic zinc carbonate, 9g of ammonium bicarbonate and 15g of ammonium sulfate, dissolving in 120g of ammonia water solution, and stirring at 50 ℃ until the solution is completely dissolved;
8) Adding the solution obtained in the step 7) into 100g of activated carbon powder, uniformly stirring at room temperature, and then drying in a drying oven at 180 ℃ for 24 hours to obtain impregnated activated carbon powder;
9) Grinding and mixing the zirconium-based multi-component metal material obtained in the step 6) and the impregnated activated carbon powder obtained in the step 8) for 10min in a ratio of 3:1;
10 The mixed powder of step 9) was added to 6% TEDA, then sealed and left at 60 ℃ for 4h.
11 And (3) bonding and molding the mixed powder obtained in the step 10) by adopting silica sol, and preparing porous zirconium carbon adsorption material particles with the diameter of 0.6-1.2 mm for standby.
Example 2
1) 200g of hydrous zirconia is weighed, 1200g of deionized water is added, and the mixture is stirred into slurry at 25 ℃;
2) Weighing 50g of potassium hydroxide, adding 50g of deionized water, and stirring until the potassium hydroxide is dissolved;
3) Slowly adding the solution obtained in the step 2) into the solution obtained in the step 1), adjusting the pH of the whole slurry to 9-11, and stirring for 3h at 25 ℃;
4) 100g of zinc sulfate and 25g of cobalt sulfate are weighed, 500g of deionized water is added, and stirring is carried out at 25 ℃ until the solution is dissolved;
5) Dropwise adding the solution of 4) into the mixed slurry added in 3) at a speed of 3 drops/s, simultaneously adding the solution of 2) in an auxiliary way, enabling the pH of the slurry to be 9-11, and then stirring for 3h at 25 ℃;
6) Filtering the slurry of the step 5), cleaning the slurry with 2000g of deionized water for 3 times, and drying the slurry at 60 ℃ for 8 hours to obtain a zirconium-based multi-component metal material;
7) Weighing 20g of basic copper carbonate, 2g of basic zinc carbonate, 9g of ammonium bicarbonate and 15g of ammonium sulfate, dissolving in 120g of ammonia water solution, and stirring at 50 ℃ until the solution is completely dissolved;
8) Adding the solution obtained in the step 7) into 100g of activated carbon powder, uniformly stirring at room temperature, and then drying in a drying oven at 180 ℃ for 24 hours to obtain impregnated activated carbon powder;
9) Grinding and mixing the zirconium-based multi-component metal material obtained in the step 6) and the impregnated activated carbon powder obtained in the step 8) for 10min in a ratio of 3:1;
10 The mixed powder of step 9) was added to 6% TEDA, then sealed and left at 60 ℃ for 4h.
11 And (3) bonding and molding the mixed powder obtained in the step 10) by adopting silica sol, and preparing the mixed powder into particles with the diameter of 0.6-1.2 mm for standby.
Example 3
1) 200g of hydrous zirconia is weighed, 1200g of deionized water is added, and the mixture is stirred into slurry at 25 ℃;
2) Weighing 50g of potassium hydroxide, adding 50g of deionized water, and stirring until the potassium hydroxide is dissolved;
3) Slowly adding the solution obtained in the step 2) into the solution obtained in the step 1), adjusting the pH of the whole slurry to 9-11, and stirring for 3h at 25 ℃;
4) 120g of zinc sulfate and 28g of cobalt sulfate are weighed, 500g of deionized water is added, and stirring is carried out at 25 ℃ until the solution is dissolved;
5) Dropwise adding the solution of 4) into the mixed slurry added in 3) at a speed of 3 drops/s, simultaneously adding the solution of 2) in an auxiliary way, enabling the pH of the slurry to be 9-11, and then stirring for 3h at 25 ℃;
6) Filtering the slurry of the step 5), cleaning the slurry with 2000g of deionized water for 3 times, and drying the slurry at 60 ℃ for 8 hours to obtain a zirconium-based multi-component metal material;
7) Weighing 20g of basic copper carbonate, 2g of basic zinc carbonate, 9g of ammonium bicarbonate and 15g of ammonium sulfate, dissolving in 120g of ammonia water solution, and stirring at 50 ℃ until the solution is completely dissolved;
8) Adding the solution obtained in the step 7) into 100g of activated carbon powder, uniformly stirring at room temperature, and then drying in a drying oven at 180 ℃ for 24 hours to obtain impregnated activated carbon powder;
9) Grinding and mixing the zirconium-based multi-component metal material obtained in the step 6) and the impregnated activated carbon powder obtained in the step 8) for 10min in a ratio of 6:1;
10 The mixed powder of step 9) was added to 6% TEDA, then sealed and left at 60 ℃ for 4h.
11 And (3) bonding and molding the mixed powder obtained in the step 10) by adopting silica sol, and preparing the mixed powder into particles with the diameter of 0.6-1.2 mm for standby.
Example 4
1) 200g of hydrous zirconia is weighed, 1200g of deionized water is added, and the mixture is stirred into slurry at 25 ℃;
2) Weighing 50g of potassium hydroxide, adding 50g of deionized water, and stirring until the potassium hydroxide is dissolved;
3) Slowly adding the solution obtained in the step 2) into the solution obtained in the step 1), adjusting the pH of the whole slurry to 9-11, and stirring for 3h at 25 ℃;
4) 160g of zinc sulfate and 30g of cobalt sulfate are weighed, 500g of deionized water is added, and stirring is carried out at 25 ℃ until the solution is dissolved;
5) Dropwise adding the solution of 4) into the mixed slurry added in 3) at a speed of 3 drops/s, simultaneously adding the solution of 2) in an auxiliary way, enabling the pH of the slurry to be 9-11, and then stirring for 3h at 25 ℃;
6) Filtering the slurry of the step 5), cleaning the slurry with 2000g of deionized water for 3 times, and drying the slurry at 60 ℃ for 8 hours to obtain a zirconium-based multi-component metal material;
7) Weighing 20g of basic copper carbonate, 2g of basic zinc carbonate, 9g of ammonium bicarbonate and 15g of ammonium sulfate, dissolving in 120g of ammonia water solution, and stirring at 50 ℃ until the solution is completely dissolved;
8) Adding the solution obtained in the step 7) into 100g of activated carbon powder, uniformly stirring at room temperature, and then drying in a drying oven at 180 ℃ for 24 hours to obtain impregnated activated carbon powder;
9) Grinding and mixing the zirconium-based multi-component metal material obtained in the step 6) and the impregnated activated carbon powder obtained in the step 8) for 10min in a ratio of 3:1;
10 The mixed powder of step 9) was added to 6% TEDA, then sealed and left at 60 ℃ for 4h.
11 And (3) bonding and molding the mixed powder obtained in the step 10) by adopting silica sol, and preparing the mixed powder into particles with the diameter of 0.6-1.2 mm for standby.
Example 5
1) 200g of hydrous zirconia is weighed, 1200g of deionized water is added, and the mixture is stirred into slurry at 25 ℃;
2) Weighing 50g of potassium hydroxide, adding 50g of deionized water, and stirring until the potassium hydroxide is dissolved;
3) Slowly adding the solution obtained in the step 2) into the solution obtained in the step 1), adjusting the pH of the whole slurry to 9-11, and stirring for 3h at 25 ℃;
4) 120g of zinc sulfate and 28g of cobalt sulfate are weighed, 500g of deionized water is added, and stirring is carried out at 25 ℃ until the solution is dissolved;
5) Dropwise adding the solution of 4) into the mixed slurry added in 3) at a speed of 3 drops/s, simultaneously adding the solution of 2) in an auxiliary way, enabling the pH of the slurry to be 9-11, and then stirring for 3h at 25 ℃;
6) Filtering the slurry of the step 5), cleaning the slurry with 2000g of deionized water for 3 times, and drying the slurry at 60 ℃ for 8 hours to obtain a zirconium-based multi-component metal material;
7) Weighing 20g of basic copper carbonate, 2g of basic zinc carbonate, 9g of ammonium bicarbonate and 15g of ammonium sulfate, dissolving in 120g of ammonia water solution, and stirring at 50 ℃ until the solution is completely dissolved;
8) Adding the solution obtained in the step 7) into 100g of activated carbon powder, uniformly stirring at room temperature, and then drying in a drying oven at 180 ℃ for 24 hours to obtain impregnated activated carbon powder;
9) Grinding and mixing the zirconium-based multi-component metal material obtained in the step 6) and the impregnated activated carbon powder obtained in the step 8) for 10min in a ratio of 5:1;
10 The mixed powder of step 9) was added to 6% TEDA, then sealed and left at 60 ℃ for 4h.
11 And (3) bonding and molding the mixed powder obtained in the step 10) by adopting silica sol, and preparing the mixed powder into particles with the diameter of 0.6-1.2 mm for standby.
Comparative example
Commercially available impregnated activated carbon materials.
The adsorption materials prepared in examples 1 to 5 were tested for protection time against sulfur dioxide, ammonia, hydrogen sulfide, benzene, hydrocyanic acid, and cyanogen chloride. And comparing with the impregnated active component active carbon material:
sulfur dioxide: specific speed 0.25L/min cm 2 The initial concentration of sulfur dioxide with the height of 2.5cm is 4.3mg/L
Ammonia gas: specific speed 0.25L/min cm 2 The initial concentration of ammonia gas with the height of 2.5cm is 2.6mg/L
Hydrogen sulfide: specific speed 0.25L/min cm 2 Initial concentration of hydrogen sulfide with height of 2.5cm is 4.3mg/L
Benzene: specific speed 0.25L/min cm 2 Benzene gas initial concentration 9mg/L with height of 2.5cm
Hydrocyanic acid: specific speed 0.25L/min cm 2 The initial concentration of hydrocyanic acid with the height of 2.5cm is 8mg/L
Cyanogen chloride: specific speed 0.25L/min cm 2 The initial concentration of hydrocyanic acid with the height of 2.5cm is 9mg/L
TABLE 1 hydrocyanic acid, cyanogen chloride, sulfur dioxide, ammonia, hydrogen sulfide, benzene protection schedule
From table 1 above, it can be seen that the porous zirconium charcoal adsorbent prepared by the present patent has better protection capability to physical adsorption type gas benzene molecules, acid gas sulfur dioxide, hydrogen sulfide, alkaline molecular ammonia gas, military chemical catalytic type toxic agents hydrocyanic acid, cyanogen chloride and other molecules, while the impregnating activated carbon sold at present has almost no protection capability to ammonia gas.
Claims (5)
1. The preparation method of the porous zirconium carbon adsorption material is characterized by comprising the following steps of:
step one, preparing a zirconium-based multi-element metal material:
a. weighing hydrous zirconia, adding deionized water, and stirring to obtain slurry, wherein the mass ratio of the hydrous zirconia to the deionized water is 1:6;
b. weighing alkaline substances, adding deionized water, and stirring until the alkaline substances are dissolved, wherein the mass ratio of the alkaline substances to the deionized water is 2-7:2-8;
c. slowly adding the solution obtained in the step (b) into the solution obtained in the step (a), regulating the pH of the whole slurry to 9-11, and stirring for 1-6 h;
d. weighing zinc sulfate and cobalt sulfate, adding deionized water, and stirring until the zinc sulfate, the cobalt sulfate and the deionized water are dissolved, wherein the mass ratio of the zinc sulfate to the cobalt sulfate to the deionized water is 10-200:1-60:300-800;
e. dropwise adding the solution in the step d into the mixed slurry added in the step c at the speed of 1-6 drops/s, simultaneously adding the solution in the step b in an auxiliary way to ensure that the pH of the slurry is 9-11, and then stirring for 2-8 h;
f. filtering the slurry obtained in the step one, cleaning the slurry with deionized water for 3 times, and drying the slurry at 40-100 ℃ for 3-12 hours to obtain a zirconium-based multi-component metal material;
step two, preparing impregnated activated carbon powder with metal active components:
a. weighing basic copper carbonate, basic zinc carbonate, ammonium bicarbonate and ammonium sulfate, dissolving in an ammonia water solution, and stirring until the basic copper carbonate, the basic zinc carbonate, the ammonium bicarbonate, the ammonium sulfate and the ammonia water are completely dissolved, wherein the mass ratio of the basic copper carbonate to the basic zinc carbonate to the ammonium bicarbonate to the ammonium sulfate to the ammonia water is (2-40) 0.01-10 g: 5-30: 1-40: 120;
b. adding the solution obtained in the step two into active carbon powder, uniformly stirring at room temperature, and then drying in an oven for 24 hours to obtain impregnated active carbon powder, wherein the mass ratio of ammonia water to active carbon powder is 6:5;
step three, preparing a porous zirconium carbon adsorption material:
a. grinding and mixing the zirconium-based multi-component metal material obtained in the step one and the impregnated activated carbon powder obtained in the step two for 5-60 min, wherein the ratio of the zirconium-based multi-component metal material to the impregnated activated carbon powder is 3-6:1-6;
b. adding the mixed powder obtained in the step (a) into triethylene diamine, sealing, and standing at 60 ℃ for 4 hours, wherein the mass of the triethylene diamine is 1-15% of that of the mixed powder obtained in the step (a);
c. and d, bonding and molding the mixed powder obtained in the step b by adopting a binder, and preparing particles with the thickness of 0.6-1.2 mm to obtain the porous zirconium carbon adsorption material.
2. The method for preparing the porous zirconium carbon adsorption material according to claim 1, wherein the stirring temperature in the first step is 25-40 ℃; the stirring temperature in the second step a is 30-65 ℃, and the drying temperature in the second step b is 140-200 ℃.
3. The method for preparing a porous zirconium carbon adsorbing material as set forth in claim 1, wherein the alkaline substance in the step b is potassium hydroxide or sodium hydroxide.
4. The method for preparing a porous zirconium carbon adsorbing material according to claim 1, wherein the zinc sulfate in the step d is replaced by one or more of zinc nitrate and zinc chloride, and the cobalt sulfate in the step d is replaced by cobalt chloride or cobalt nitrate.
5. The method for preparing a porous zirconium carbon adsorption material according to claim 1, wherein the binder in the step two c is one of silica sol, tar, polyvinyl alcohol and hydroxymethyl fiber.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9308517B1 (en) * | 2013-03-15 | 2016-04-12 | The United States Of America As Represented By The Secretary Of The Army | Composite filtration media for removing broad spectrum toxic chemicals |
| CN106513004A (en) * | 2016-10-31 | 2017-03-22 | 山西新华化工有限责任公司 | Zirconium-loaded impregnation carbon defending against HCN and CNCl toxic agents and preparation method thereof |
| US9895674B1 (en) * | 2015-09-14 | 2018-02-20 | The United States Of America As Represented By The Secretary Of The Army | Multi-functional media for the removal of basic and acidic gases and other toxic vapors |
| CN108097210A (en) * | 2017-12-19 | 2018-06-01 | 海宁瑞创新材料有限公司 | A kind of preparation method of nano-metal-oxide and porous active carbon composite material |
| KR20180105620A (en) * | 2018-09-17 | 2018-09-28 | 한소 주식회사 | Iron-zinc complex metal oxide coated activated carbon adsorbent for acidic gas removal and manufacturing method the same |
| CN111389354A (en) * | 2020-03-04 | 2020-07-10 | 山西新华化工有限责任公司 | Preparation method of broad-spectrum protection impregnated activated carbon |
| CN112427017A (en) * | 2020-11-23 | 2021-03-02 | 华东理工大学 | Preparation method of porous modified activated carbon-alumina composite desulfurization adsorbent |
| CN112791699A (en) * | 2021-01-20 | 2021-05-14 | 辽宁科技大学 | A kind of preparation method of ZrO2/coal tar-based composite activated carbon ball |
| CN113101891A (en) * | 2021-04-16 | 2021-07-13 | 中北大学 | A kind of high nitrogen carbon-based zirconium phosphate broad-spectrum gas adsorbent and its preparation method and application |
-
2021
- 2021-09-10 CN CN202111059099.9A patent/CN113648971B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9308517B1 (en) * | 2013-03-15 | 2016-04-12 | The United States Of America As Represented By The Secretary Of The Army | Composite filtration media for removing broad spectrum toxic chemicals |
| US9895674B1 (en) * | 2015-09-14 | 2018-02-20 | The United States Of America As Represented By The Secretary Of The Army | Multi-functional media for the removal of basic and acidic gases and other toxic vapors |
| CN106513004A (en) * | 2016-10-31 | 2017-03-22 | 山西新华化工有限责任公司 | Zirconium-loaded impregnation carbon defending against HCN and CNCl toxic agents and preparation method thereof |
| CN108097210A (en) * | 2017-12-19 | 2018-06-01 | 海宁瑞创新材料有限公司 | A kind of preparation method of nano-metal-oxide and porous active carbon composite material |
| KR20180105620A (en) * | 2018-09-17 | 2018-09-28 | 한소 주식회사 | Iron-zinc complex metal oxide coated activated carbon adsorbent for acidic gas removal and manufacturing method the same |
| CN111389354A (en) * | 2020-03-04 | 2020-07-10 | 山西新华化工有限责任公司 | Preparation method of broad-spectrum protection impregnated activated carbon |
| CN112427017A (en) * | 2020-11-23 | 2021-03-02 | 华东理工大学 | Preparation method of porous modified activated carbon-alumina composite desulfurization adsorbent |
| CN112791699A (en) * | 2021-01-20 | 2021-05-14 | 辽宁科技大学 | A kind of preparation method of ZrO2/coal tar-based composite activated carbon ball |
| CN113101891A (en) * | 2021-04-16 | 2021-07-13 | 中北大学 | A kind of high nitrogen carbon-based zirconium phosphate broad-spectrum gas adsorbent and its preparation method and application |
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