CN114870803A - Arsine-phosphine special gas adsorbent and preparation method thereof - Google Patents

Arsine-phosphine special gas adsorbent and preparation method thereof Download PDF

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CN114870803A
CN114870803A CN202210584093.1A CN202210584093A CN114870803A CN 114870803 A CN114870803 A CN 114870803A CN 202210584093 A CN202210584093 A CN 202210584093A CN 114870803 A CN114870803 A CN 114870803A
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arsine
phosphine
component
gas adsorbent
activated carbon
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陈逵
金大正
周育呈
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Changzhou Chengerzheng Environmental Protection Technology Co ltd
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Changzhou Chengerzheng Environmental Protection Technology Co ltd
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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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The application relates to the technical field of waste gas adsorbents, and particularly discloses an arsine-phosphine special gas adsorbent and a preparation method thereof, wherein the adsorbent comprises a component A and a component B, and the volume ratio of the component A to the component B is 1: (0.1-0.3); the component A comprises the following raw materials in percentage by weight: nano active copper oxide, active aluminum oxide and silicon dioxide; the specific surface area of the nano active copper oxide is more than 100m 2/g; the specific surface area of the nano active copper oxide is more than 100m 2/g; the component B is aluminum sol. The specific surface area and the pore volume of the arsine-phosphane special gas adsorbent of the waste gas adsorbent obtained by the application are respectively 120m2/g and 0.50cm3/g at most, and the adsorbent has higher specific surface area and pore volume; the highest adsorption capacities for arsine and phosphine are 67L/L and 117L/L respectively, so that the capacity of the arsine and phosphine adsorbent for the special gas of arsine and phosphine is improved.

Description

Arsine-phosphine special gas adsorbent and preparation method thereof
Technical Field
The application relates to the field of waste gas adsorbents, in particular to an arsine-phosphine special gas adsorbent and a preparation method thereof.
Background
The electroplating industry can produce bad plated parts or electroplating hangers, chemical polishing of aluminum alloy and stainless steel, silicon wafer treatment in photovoltaic industry, combustion in boilers, brick kilns, chemical engineering and other production processes.
Special gases, also called special gases, are basic chemical raw materials with high dangerousness, most of which are flammable, explosive, toxic and corrosive gases, and therefore special treatment is needed in the production process to reduce the harm of the special gases to human bodies and the environment. Common characteristic gases are chlorine, hydrochloric acid, nitrogen dioxide, sulfur dioxide, phosphane, arsane and volatile organic compounds. The phosphane is also called phosphine and the arsane is also called arsine, and the phosphane and the arsine are mainly generated in the semiconductor industrial production engineering, are colorless gases with foul smell at normal temperature, have strong toxicity and damage the health of human bodies after being inhaled. In addition, the phosphane and the arsane are combustible gases, so that fire disasters are easy to occur. Therefore, the purification of arsine and phosphine gases is of great importance in industrial production.
The arsine-phosphane special gas adsorbent is an adsorbent for purifying arsine and phosphane special gas, can effectively adsorb arsine and phosphane from gas or liquid and react with the arsine and the phosphane to generate stable compounds such as harmless calcium salts and the like, reduces the damage of the arsine-phosphane to human bodies and the environment, and is widely applied to the fields of solar batteries, electric power, LED manufacturing industry, LCD manufacturing industry, pharmaceutical and chemical industry, semiconductor chip manufacturing and the like. At present, the arsine and phosphine special gas adsorbent produced by the related technology has weaker adsorption capacity, and can reach the emission standard of the arsine and phosphine special gas only by using larger amount of the arsine and phosphine special gas adsorbent and longer adsorption time.
Disclosure of Invention
In order to improve the adsorption capacity of the arsine and phosphine special gas adsorbent, the application provides the arsine and phosphine special gas adsorbent and the preparation method thereof.
In a first aspect, the present application provides an arsine phosphine special gas adsorbent, which adopts the following technical scheme:
an arsine phosphine special gas adsorbent comprises a component A and a component B, wherein the volume ratio of the component A to the component B is 1: (0.1-0.3); the component A comprises the following raw materials in percentage by weight: 70-90% of nano active copper oxide, 5-15% of active aluminum oxide and 5-15% of silicon dioxide; the specific surface area of the nano active copper oxide is more than 100m 2 (ii)/g; the component B is aluminum sol.
By adopting the technical scheme, the arsine and the phosphine are reducing gases, the nano active copper oxide can be subjected to oxidation-reduction reaction with the arsine and the phosphine to be converted into high-valence arsenic compounds or phosphorus compounds and other nontoxic or low-toxicity substances,thereby playing a role in treating and purifying the arsine and phosphine special gas. The activated alumina has the characteristics of high functional group density, porosity, high dispersibility, insulativity, heat resistance and the like on the surface, can increase the pore size number of the arsine and phosphine special gas adsorbent, and is beneficial to forming the arsine and phosphine special gas adsorbent. The silicon dioxide has high adsorption performance, good thermal stability, stable chemical property, higher mechanical strength and the like, can be used as a catalyst, and improves the adsorption performance of the arsine and phosphine special gas adsorbent; in addition, the silicon dioxide can also adjust the density of the copper oxide and reduce the density of the copper oxide, thereby being more beneficial to the reaction of phosphine and arsine. The specific surface area of the nano active copper oxide is more than 100m 2 The specific surface area of the arsine and phosphine special gas adsorbent can be ensured, so that the adsorption performance of the arsine and phosphine special gas adsorbent is improved.
Preferably, the method comprises the following steps: the component A comprises the following raw materials in percentage by weight: 75-85% of nano active copper oxide, 8-12% of active aluminum oxide and 8-12% of silicon dioxide.
Preferably, the method comprises the following steps: the active copper oxide is obtained by modification pretreatment; the specific operation steps of the modification pretreatment of the nano active copper oxide are as follows: soaking the nano active copper oxide into a tetrahydrate manganese acetate solution, stirring for 2-3h, drying, calcining for 3-4h at 400 +/-5 ℃, cooling, and crushing to 350-400 meshes to obtain modified nano active copper oxide; the concentration of the manganese acetate tetrahydrate solution is 0.05 mol/L; the dosage of the nano active copper oxide is 10-20% of the manganese acetate tetrahydrate solution.
By adopting the scheme, the nano active copper oxide is soaked in the manganese acetate tetrahydrate solution, so that the trimanganese tetroxide is loaded on the nano active copper oxide to modify the nano active copper oxide, the activity and the specific surface area of the nano active copper oxide are improved, and the adsorption capacity of the nano active copper oxide on the arsine and phosphane special gas is further improved.
Preferably, the method comprises the following steps: the component A also comprises the following raw materials in percentage by weight: 3-7% of nickel oxide and 1-2% of silanized graphene.
By adopting the technical scheme, the nickel oxide has higher specific surface area, large pore volume and higher adsorption capacity, and can increase the pore size number of the arsine-phosphine special gas adsorbent. The graphene has a large specific surface area, large adsorption capacity, thin mechanical strength and high mechanical strength, but the graphene lamellar layers have strong van der Waals force, so that the graphene lamellar layers are easy to gather, and the silanized graphene improves the dispersity and stability of the graphene in the arsine and phosphine special gas adsorbent and simultaneously prevents the arsine and phosphine special gas adsorbent from caking; the adsorption capacity of the arsine and phosphine special gas adsorbent can be further improved.
Preferably, the method comprises the following steps: the component A also comprises 1-3 wt% of modified honeycomb activated carbon;
the specific preparation method of the modified honeycomb activated carbon comprises the following steps: grinding the honeycomb activated carbon to 350-400 meshes, washing the honeycomb activated carbon with clear water, adding deionized water to boil, stirring for 1-2h, filtering, drying, soaking the dried honeycomb activated carbon in 1mol/L sodium hydroxide solution for 6-8h, washing with clear water, filtering, soaking the filtered honeycomb activated carbon in 20% sulfur solution, and calcining at 500 +/-5 ℃ for 3-4h to obtain modified honeycomb activated carbon; the volume ratio of the honeycomb activated carbon to the sodium hydroxide solution is 1: (20-30); the volume ratio of the honeycomb activated carbon to the sulfur solution is 1: (18-22).
By adopting the technical scheme, the honeycomb activated carbon is prepared by carbonizing and activating carbon-containing raw materials such as charcoal, fruit shells, coal and the like. The activated carbon has the advantages of fine pores in the activated carbon, low bulk density, large specific surface area, full contact and adsorption with phosphane and arsane gases, more capillaries in the carbon granules and stronger adsorption capacity.
In the modification process, the honeycomb activated carbon is subjected to boiling pretreatment, so that the adsorption period of the activated carbon is prolonged, and the adsorption efficiency of the activated carbon is improved. And soaking the filtered honeycomb activated carbon in a sodium hydroxide solution, and carrying out reduction modification on functional groups on the surface of the honeycomb activated carbon to improve the content of basic groups, so that the non-polarity of the activated carbon is increased, and the adsorption capacity of the activated carbon on special gases of arsine and phosphine is improved. And finally, soaking the honeycomb activated carbon soaked in the sodium hydroxide solution in a copper sulfate solution to load sulfur ions on the honeycomb activated carbon, so that the adsorption capacity of the honeycomb activated carbon on the arsine and phosphine special gas is improved, and the adsorption capacity of the arsine and phosphine special gas adsorbent is improved.
Preferably, the method comprises the following steps: the iodine value of the honeycomb activated carbon is 800 mg/g.
By adopting the technical scheme, the iodine value of the honeycomb activated carbon is an important index for measuring the adsorption capacity of the honeycomb activated carbon, and the honeycomb activated carbon with higher iodine value has higher activation degree and higher adsorption capacity.
Preferably, the method comprises the following steps: the component A also comprises 0.5 to 1 weight percent of stabilizing additive; the stabilizing additive is a mixture of sodium persulfate and sodium hypochlorite, and the volume ratio of the sodium persulfate to the sodium hypochlorite is 1: (1-3).
By adopting the technical scheme, the sodium persulfate can oxidize the arsine into non-toxic or low-toxic substances. Sodium hypochlorite oxidizes the phosphane and converts it to sodium hypophosphite. Improves the recovery rate of phosphorus resources and reduces the influence of phosphane on the atmospheric environment and the human health. However, the use of sodium hypochlorite for treating phosphine can generate a large amount of environmental pollutants such as a side reactant chlorine and the like.
In a second aspect, the present application provides a method for preparing any one of the arsine and phosphine special gas adsorbents, which is specifically realized by the following technical scheme:
a preparation method of an arsine and phosphine special gas adsorbent comprises the following operation steps:
grinding the raw materials of the arsine phosphine special gas adsorbent to the particle size of 350-400 meshes, and uniformly mixing to obtain a component A; and mixing the component A and the alumina sol in proportion, stirring uniformly, extruding, granulating, drying to obtain the arsine-phosphine special gas adsorbent, wherein the particle length is 3-15mm, and the particle size is 3-5 mm.
By adopting the scheme, the component A is mixed with the alumina sol, so that the arsine-phosphine special gas adsorbent is formed and is not loosened, and the later-stage extrusion granulation is facilitated.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) the application controls the types and the mixing amount of raw materials of the arsine and phosphine special gas adsorbent to ensure that arsine is mixed with the special gas adsorbentThe specific surface area and the pore volume of the phosphane special gas adsorbent and the adsorption capacities of arsane and phosphane are respectively 103m 2 /g、0.41cm 3 The adsorption capacity is higher than that of the adsorbent, such as/g, 53L/L and 98L/L.
(2) According to the application, the specific surface area, the pore volume and the adsorption capacity of the arsine and phosphine special gas adsorbent are respectively 106m by modifying and pretreating the nano active copper oxide 2 /g、0.42cm 3 The specific adsorption capacity of the arsine and phosphine gas adsorbent is further improved, namely the specific adsorption capacity of arsine and phosphine gas adsorbent is 99L/L.
(3) The specific surface area and the pore volume of the arsine and phosphine special gas adsorbent and the adsorption capacities of arsine and phosphine are respectively 107m by modifying and pretreating activated alumina 2 /g、0.44cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphine and the phosphine in the adsorbent is 54L/L and 101L/L.
(4) According to the application, the specific surface area, the pore volume and the adsorption capacities of the arsine and phosphine are respectively 109m by adding the nickel oxide and the silanized graphene into the raw material component A of the arsine and phosphine special gas adsorbent 2 /g、0.45cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphine and the phosphine in the adsorbent is 56L/L and 105L/L.
(5) According to the method, nickel oxide and silanized graphene are pretreated, so that the specific surface area and the pore volume of the arsine and phosphine special gas adsorbent and the adsorption capacities of arsine and phosphine are 111m respectively 2 /g、0.46cm 3 The adsorption capacity of the arsine phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphorus and the arsenic in the adsorbent per gram, 58L/L and 107L/L.
(6) The specific surface area, the pore volume and the adsorption capacities of the arsine and phosphine special gas adsorbent are respectively 114m by adding the modified honeycomb activated carbon into the raw material component A of the arsine and phosphine special gas adsorbent and controlling the mixing amount of the modified honeycomb activated carbon 2 /g、0.47cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphine and the phosphine in the adsorbent is 62L/L and 110L/L.
(7) The specific surface area and the pore body of the arsine-phosphine special gas adsorbent are enabled to be limited to 800mg/g by limiting the iodine value of the honeycomb activated carbon to be 800mg/gThe adsorption capacities of product, arsine and phosphine were 115m 2 /g、0.48cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphorus and the phosphine in the adsorbent is 63L/L and 112L/L.
(8) The specific surface area, the pore volume and the adsorption capacities of the arsine and phosphine special gas adsorbent are respectively 117m by adding the stabilizing additive into the raw material component A of the arsine and phosphine special gas adsorbent and controlling the mixing amount of the stabilizing additive 2 /g、0.49cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is further improved by the concentration of the arsenic, the phosphine and the phosphine in the adsorbent is 65L/L and 115L/L.
(9) The specific surface area, the pore volume and the adsorption capacity of the arsine and phosphine are respectively 120m by regulating the volume ratio of the sodium persulfate to the sodium hypochlorite 2 /g、0.50cm 3 The adsorption capacity of the arsine and phosphine special gas adsorbent is improved by/g, 67L/L and 117L/L.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials are all commercially available products, and are all sufficient for disclosure of the raw materials in the present application, and should not be construed as limiting the source of the raw materials. The method specifically comprises the following steps: copper oxide, specific surface area 100m 2 (ii)/g; alumina, catalyst grade, particle size 1-3 mm; silica with particle size of 325 meshes; ferric oxide with the grain size of 325 meshes; chromium diboride with a purity of 99%; palladium nitrate dihydrate, Pd is more than or equal to 39.0%; silanized graphene with a thickness of 1-5 nm; the iodine values of the honeycomb activated carbon are 800mg/g and 500mg/g respectively; sodium persulfate with a particle size of 50 meshes; sodium hypochlorite in the form of granules.
The following examples of the preparation of the stabilizing assistant
Preparation example 1
The preparation of the stabilizing additive in the application is prepared by the following operation steps: according to the mixing amount shown in the table 1, sodium persulfate and sodium hypophosphite are crushed to 350 meshes of particle size and mixed uniformly to obtain the stabilizing additive.
Preparation examples 2 to 4
The stabilizing additives of preparation examples 2 to 4 were identical to those of preparation example 1 in the preparation method and the types of raw materials, except for the blending amount of each raw material, which is specifically shown in table 1.
TABLE 1 amounts of raw materials (unit: kg) of Adamahosphoalkane specialty gas adsorbents of production examples 1 to 4
Raw materials Preparation example 1 Preparation example 2 Preparation example 3 Preparation example 4
Sodium persulfate 20 10 10 20
Sodium hypochlorite 20 20 30 10
Example 1
The arsine phosphate carbon sorbent of example 1, prepared by the following steps:
according to the mixing amount of the table 2, the specific surface area is 100m 2 Grinding/g of nano active copper oxide, active aluminum oxide and silicon dioxide to 350 meshes of particle size, mixing uniformly,obtaining a mixture A;
and mixing the mixture A and the aluminum sol according to the volume ratio of 1:0.2, uniformly stirring, extruding, granulating to obtain particles with the length of 3mm and the particle size of 3mm, and drying to obtain the arsine-phosphine special gas adsorbent.
Examples 2 to 3
The arsine and phosphine special gas adsorbents of examples 2 to 3 have the same preparation method and the same types of raw materials as those of example 1, except for the amount of each raw material, and are specifically shown in Table 2.
TABLE 2 raw material blending amounts (unit: kg) of the arsine phosphine specialty gas adsorbents of examples 1-3
Raw materials Example 1 Example 2 Example 3
Nano active copper oxide 70 80 90
Activated alumina 15 10 5
Silicon dioxide 15 10 5
Example 4
The preparation method and the raw material mixing amount of the arsine and phosphine special gas adsorbent in the embodiment 4 are the same as those in the embodiment 2, except that the activated copper oxide is obtained by modification pretreatment; the specific operation steps of the modification pretreatment of the nano active copper oxide are as follows: soaking the nano active copper oxide into a tetrahydrate manganese acetate solution, stirring for 2 hours, drying, calcining for 4 hours at 400 ℃, cooling, and crushing to 350 meshes to obtain modified nano active copper oxide; the concentration of the manganese acetate tetrahydrate solution is 0.05 mol/L; the dosage of the nano active copper oxide is 10 percent of the tetrahydrate manganese acetate solution, and the modified nano active copper oxide is obtained.
Example 5
The arsine phosphine sorbent of example 5 was prepared using the same procedure and starting materials as in example 4, except that the activated copper oxide was obtained by a modified pretreatment; the specific operation steps of the modification pretreatment of the nano active copper oxide are as follows: soaking the nano active copper oxide into a manganese dioxide solution, stirring for 2h, drying, calcining at 400 ℃ for 4h, cooling, and crushing to 350 meshes to obtain modified nano active copper oxide; the concentration of the manganese dioxide solution is 0.05 mol/L; the dosage of the nano active copper oxide is 10 percent, and the modified nano active copper oxide is obtained.
Examples 6 to 10
The arsine and phosphine special gas adsorbents of examples 6 to 10 are completely the same as the preparation method of example 5, except that nickel and silanized graphene are also added into the raw materials, and the specific mixing amount is shown in table 3.
TABLE 3 raw material blending amounts (unit: kg) of the arsine phosphine specialty gas adsorbents of examples 6-10
Raw materials Example 6 Example 7 Example 8 Example 9 Example 10
Nano active copper oxide 80 80 80 80 80
Activated alumina 5 5 5 5 5
Silicon dioxide 11 9 7 8.5 8
Nickel oxide 3 5 7 5 5
Silanized graphene 1 1 1 1.5 2
Example 11
The preparation method and the raw material mixing amount of the arsine and phosphine special gas adsorbent in the embodiment 11 are the same as those in the embodiment 9, except that the silanized graphene is replaced by the oxidized graphene in the same amount, and the types of the other raw materials are completely the same as those in the embodiment 9.
Examples 12 to 14
The arsine phosphine special gas adsorbents of examples 12 to 14 are completely the same as the adsorbents of example 9 in preparation method, except that modified honeycomb activated carbon is also added into the raw materials, and the specific preparation method of the modified honeycomb activated carbon is as follows: grinding honeycomb activated carbon with an iodine value of 500mg/g to 350 meshes, washing the honeycomb activated carbon with clear water, adding deionized water to boil, stirring for 2 hours, filtering, drying, placing the dried honeycomb activated carbon in 1mol/L sodium hydroxide solution to be soaked for 8 hours, wherein the volume ratio of the honeycomb activated carbon to the sodium hydroxide solution is 1: 25, washing with clear water, filtering, and then soaking the filtered honeycomb activated carbon in a sulfur solution with the concentration of 20%, wherein the volume ratio of the honeycomb activated carbon to the chromium solution is 1: calcining at 20 ℃ and 500 ℃ for 3h to obtain the modified honeycomb activated carbon, wherein the specific mixing amount is shown in Table 4.
TABLE 4 raw material contents (unit: kg) of the arsine phosphine specialty gases adsorbents of examples 12-14
Raw materials Example 12 Example 13 Example 14
Nano active copper oxide 80 80 80
Activated alumina 5 5 5
Silicon dioxide 7.5 6.5 5.5
Nickel oxide 5 5 5
Silanized graphene 1.5 1.5 1.5
Modified honeycomb activated carbon 1 2 3
Example 15
The arsine phosphine specific gas adsorbent of example 15 was prepared in the same manner and in the same amount as in example 13 except that the iodine value of the honeycomb activated carbon in the raw material was 800mg/g, and the kind and amount of the other raw materials were the same as in example 13.
Example 16
The arsine phosphine special gas adsorbent of example 16 was prepared in the same manner and in the same amount as in example 15 except that the modified honeycomb activated carbon was replaced with the modified activated carbon in the same amount as in example 15, and the kind and the amount of the other raw materials were the same as in example 15.
Examples 17 to 19
The arsine and phosphine special gas adsorbents of examples 17 to 19 are identical to the preparation method of example 15, except that the stabilizing additive prepared in preparation example 1 is further added to the raw materials, the types and the mixing amount of the rest raw materials are identical to those of example 15, and the specific mixing amount is shown in Table 5.
TABLE 5 raw material blending amounts (unit: kg) of the arsine phosphine specialty gas adsorbents of examples 17-19
Starting materials Example 17 Example 18 Example 19
Nano active copper oxide 80 80 80
Activated alumina 5 5 5
Silicon dioxide 6 5.7 5.5
Nickel oxide 5 5 5
Silanized graphene 1.5 1.5 1.5
Modified honeycomb activated carbon 2 2 2
Stabilizing aid 0.5 0.8 1
Examples 20 to 22
The arsine and phosphine special gas adsorbents of examples 20 to 22 were prepared in the same manner as in example 18 except that the stabilizing assistant used in the raw materials was the stabilizing assistant prepared in preparation examples 2 to 4, and the kinds of the other raw materials were the same as in example 18.
Comparative example 1
The arsine phosphine specialty gas adsorbent of comparative example 1 was prepared exactly the same as example 1, except that: the nano active copper oxide in the raw material of the arsine and phosphine special gas adsorbent is replaced by active copper oxide, and the rest raw materials and the mixing amount are the same as those in the example 1.
Comparative example 2
The arsine phosphine specialty gas adsorbent of comparative example 2 was prepared exactly the same as example 1, except that: the specific surface area of the nano active copper oxide is 60m 2 The amount of the other raw materials and the amount of the other raw materials were the same as in example 1.
Comparative example 3
The arsine phosphine specialty gas adsorbent of comparative example 3 was prepared exactly the same as example 1, except that: the raw materials of the arsine and phosphine special gas adsorbent are not added with silicon dioxide, and the other raw materials and the mixing amount are the same as those of the example 1.
Performance detection
The following test standards or methods were used to test the performance of each of examples 1-22 and comparative examples 1-3, and the results are shown in Table 6.
Adsorption capacity: the method adopts an adsorption capacity method to perform performance characterization on the arsine-phosphine special gas adsorbent, and comprises the following specific operation steps: weighing 12g of arsine and phosphine special gas adsorbent, wherein gas components at inlets of the adsorbers are respectively 1000ppm of phosphine and 1000ppm of arsine, nitrogen is used as a carrier, adsorption isotherm data is obtained by a volumetric method, and adsorption capacities of the arsine and phosphine adsorbent for adsorbing arsine and phosphine are respectively calculated.
Specific surface area and pore size: the specific surface area and the pore diameter of the arsine-phosphine special gas adsorbent are measured by a BET method by adopting a full-automatic specific surface area and porosity analyzer.
TABLE 6 Performance test results for different arsine-phosphine adsorbents
Figure BDA0003662751410000081
Figure BDA0003662751410000091
The detection results in Table 6 show that the specific surface area and the pore volume of the arsine and phosphine special gas adsorbent obtained by the methodThe maximum adsorption capacities of arsine and phosphine are respectively 120m 2 /g、0.50cm 3 The specific surface area and pore volume are higher, and the adsorption capacity of the arsine and phosphine special gas adsorbent is improved.
In examples 1-3, the specific surface area, pore volume, and adsorption capacities of arsine and phosphine were 103m for the arsine and phosphine adsorbents of example 2, respectively 2 /g、0.41cm 3 The dosage of the nano active copper oxide in the arsenopyridine special gas adsorbent in the example 2 is more appropriate, and the nano active copper oxide can be converted into non-toxic or low-toxic substances such as high-price arsenic compounds or phosphorus compounds through oxidation-reduction reaction with arsine and phosphine, so that the effect of treating and purifying the arsenopyridine special gas is achieved, and the nano active copper oxide has a higher specific surface area.
Combining example 2 and example 4, it was found that the specific surface area, pore volume, and adsorption capacity of the arsine and phosphine adsorbents of example 4 were 106m, respectively 2 /g、0.42cm 3 The specific surface area, the pore volume and the capacity of adsorbing phosphane of the arsine-phosphane special gas adsorbent can be improved after the nano active copper oxide is subjected to modification pretreatment by using the trimanganese tetroxide, wherein the specific surface area and the pore volume of the arsine-phosphane special gas adsorbent are higher than those of the nano active copper oxide in example 2. Probably related to the modification of the nano active copper oxide by loading the trimanganese tetroxide on the nano active copper oxide, the improvement of the activity and the specific surface area of the nano active copper oxide and the further improvement of the adsorption capacity of the nano active copper oxide on the arsine and the arsine.
Combining example 4 and example 5, it was found that the specific surface area, pore volume, and adsorption capacity of arsine and phosphine of the arsine and phosphine special gas adsorbent of example 5 are all lower than those of example 4, and compared with example 4, the specific surface area, pore volume, and adsorption capacity of arsine and phosphine of the arsine and phosphine special gas adsorbent are reduced after the nano-active copper oxide is subjected to the modified pretreatment by using trimanganese tetroxide.
In examples 6 to 10, the specific surface area, pore volume, and adsorption capacities of arsine and phosphine were 109m for the arsine and phosphine adsorbents of example 9, respectively 2 /g、0.45cm 3 The specific surface area, the pore volume and the capacity of adsorbing the arsine and the phosphine can be improved by adding the nickel oxide and the silanized graphene into the raw materials of the arsine and phosphine special gas adsorbent. Probably, the silanized graphene has higher specific surface area and large pore volume, and can prevent the arsine and phosphine special gas adsorbent from caking while improving the adsorption capacity of the arsine and phosphine special gas adsorbent, so that the adsorption capacity of the arsine and phosphine special gas adsorbent can be further improved.
In combination with example 9 and example 11, it was found that the specific surface area, pore volume, and adsorption capacities of arsine and phosphine of the arsine and phosphine of example 11 were all lower than those of example 9, indicating that the adsorption capacity of the arsine and phosphine adsorbent is weaker after addition of graphene oxide than after addition of silanized graphene.
In examples 12 to 14, the specific surface area, pore volume, and adsorption capacities of arsine and phosphine of the arsine and phosphine adsorbents of example 13 were 114m, respectively 2 /g、0.47cm 3 The specific surface area, the pore volume and the capacity of adsorbing the arsine and phosphine of the special gas adsorbent are improved by the proper mixing amount of the modified honeycomb activated carbon in the raw material of the arsine and phosphine special gas adsorbent in example 13, which is shown in the specification of the embodiment 12 and example 14. Probably related to that the carbon granules of the modified honeycomb activated carbon contain more capillaries and have stronger adsorption capacity.
Combining example 13 and example 15, it was found that the specific surface area, pore volume, and adsorption capacities of arsine and phosphine were 117m for the arsine and phosphine adsorbents of example 15, respectively 2 /g、0.48cm 3 The iodine values of the limited honeycomb activated carbon are 800mg/g, and the specific surface area, the pore volume and the capacity of adsorbing the arsine and the phosphine can be improved. Probably related to the higher activation degree and higher adsorption capacity of the honeycomb activated carbon with higher iodine value.
Combining example 15 with example 16, it was found that the specific surface area, pore volume, and adsorption capacity of arsine and phosphine were all lower for the arsine and phosphine gas adsorbents of example 16 than for example 15, indicating that replacing the modified honeycomb activated carbon by an equivalent amount of modified activated carbon reduces the specific surface area, pore volume, and capacity to adsorb arsine and phosphine.
In examples 17-19, the specific surface area, pore volume, and adsorption capacities of arsine and phosphine were 117m for the arsine and phosphine adsorbents of example 18, respectively 2 /g、0.49cm 3 The specific surface area, the pore volume and the capacity of adsorbing the arsine and the phosphane of the special gas adsorbent can be improved by properly adding the stabilizing auxiliary agent in the raw materials of the arsine and phosphane special gas adsorbent in example 18. It may be associated with sodium persulfate which oxidizes arsine to non-toxic or less toxic substances and sodium hypochlorite which oxidizes and converts phosphane to sodium hypophosphite.
Combining example 17 with examples 20-22, it was found that the specific surface area, pore volume, and adsorption capacities of arsine and phosphine were 120m for the arsine and phosphine adsorbents of example 20, respectively 2 /g、0.50cm 3 The volume ratio of sodium persulfate to sodium hypochlorite in the stabilizing auxiliary agent is 1:2, so that the specific surface area, the pore volume and the capacity of adsorbing arsine and phosphine of the arsine and phosphine special gas adsorbent can be improved.
In addition, by combining various index data of the arsine phosphine special gas adsorbents in comparative examples 1-3 and example 1, the application finds that the adsorption capacity of the arsine phosphine special gas adsorbents can be improved to different degrees by adding active nano copper oxide and silicon dioxide into raw materials of the arsine phosphine special gas adsorbents and limiting the specific surface area of the active nano copper oxide.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. The arsine and phosphine special gas adsorbent is characterized by comprising a component A and a component B, wherein the volume ratio of the component A to the component B is 1: (0.1-0.3); the component A comprises the following raw materials in percentage by weight: 70-90% of nano active copper oxide, 5-15% of active aluminum oxide and 5-15% of silicon dioxide; the specific surface area of the nano active copper oxide is more than 100m 2/g; the component B is aluminum sol.
2. The arsine phosphate specialty gas adsorbent of claim 1 wherein component a comprises the following raw materials in weight percent: 75-85% of nano active copper oxide, 8-12% of active aluminum oxide and 8-12% of silicon dioxide.
3. The arsine phosphate specialty gas adsorbent of claim 1, wherein: the active copper oxide is obtained by modification pretreatment; the specific operation steps of the modification pretreatment of the nano active copper oxide are as follows: soaking the nano active copper oxide into a tetrahydrate manganese acetate solution, stirring for 2-3h, drying, calcining for 3-4h at 400 +/-5 ℃, cooling, and crushing to 350-400 meshes to obtain modified nano active copper oxide; the concentration of the manganese acetate tetrahydrate solution is 0.05 mol/L; the dosage of the nano active copper oxide is 10-20% of the manganese acetate tetrahydrate solution.
4. The arsine phosphate specialty gas adsorbent of claim 1 wherein component a further comprises the following raw materials in weight percent: 3-7% of nickel oxide and 1-2% of silanized graphene.
5. The arsine phosphine target gas adsorbent of claim 1, wherein: the component A also comprises 1-3 wt% of modified honeycomb activated carbon;
the specific preparation method of the modified honeycomb activated carbon comprises the following steps: grinding the honeycomb activated carbon to 350-400 meshes, washing the honeycomb activated carbon with clear water, adding deionized water to boil, stirring for 1-2h, filtering, drying, soaking the dried honeycomb activated carbon in 1mol/L sodium hydroxide solution for 6-8h, washing with clear water, filtering, soaking the filtered honeycomb activated carbon in 20% copper sulfate solution, and calcining at 500 +/-5 ℃ for 3-4h to obtain modified honeycomb activated carbon; the volume ratio of the honeycomb activated carbon to the sodium hydroxide solution is 1: (20-30); the volume ratio of the honeycomb activated carbon to the copper sulfate solution is 1: (18-22).
6. The arsine phosphate specialty gas adsorbent of claim 5, wherein the iodine value of the honeycomb activated carbon is 800 mg/g.
7. The arsine phosphate specialty gas adsorbent of claim 1 wherein component a further comprises 0.5 to 1 weight percent of a stabilizing additive; the stabilizing additive is a mixture of sodium persulfate and sodium hypochlorite, and the volume ratio of the sodium persulfate to the sodium hypochlorite is 1: (1-3).
8. A method of making the arsine phosphate gas sorbent of any of claims 1 to 7, comprising the steps of:
grinding the raw materials of the arsine phosphine special gas adsorbent to the particle size of 350-400 meshes, and uniformly mixing to obtain a component A; and mixing the component A and the alumina sol in proportion, stirring uniformly, extruding, granulating, drying to obtain the arsine-phosphine special gas adsorbent, wherein the particle length is 3-15mm, and the particle size is 3-5 mm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155511A (en) * 2022-09-08 2022-10-11 格林斯达(北京)环保科技股份有限公司 Preparation method of high-efficiency purifying material for hydride-containing waste gas, purifying material and application
CN115155244A (en) * 2022-08-11 2022-10-11 上海正帆科技股份有限公司 Electronic special gas purification method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155244A (en) * 2022-08-11 2022-10-11 上海正帆科技股份有限公司 Electronic special gas purification method
CN115155511A (en) * 2022-09-08 2022-10-11 格林斯达(北京)环保科技股份有限公司 Preparation method of high-efficiency purifying material for hydride-containing waste gas, purifying material and application

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