CN115155511B - Preparation method of high-efficiency purifying material for hydride-containing waste gas, purifying material and application - Google Patents
Preparation method of high-efficiency purifying material for hydride-containing waste gas, purifying material and application Download PDFInfo
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- 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
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- 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
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The application relates to the technical field of waste gas adsorption, and particularly discloses a preparation method, a purification material and application of a high-efficiency purification material for waste gas containing hydride. A preparation method of a material for efficiently purifying hydride-containing waste gas comprises the following operation steps: preparing a carrier; dissolving copper nitrate in water, stirring uniformly to obtain a copper salt solution, soaking a carrier in the copper salt solution, and drying to obtain a mixture A; preparing a sodium hydroxide aqueous solution, soaking the obtained mixture A in the sodium hydroxide aqueous solution, and drying to obtain the purifying material. The pore volume of the purification material obtained by the preparation method of the purification material is 1.26cm3/g at most, the removal rate of arsine is 100% at most, the saturated adsorption capacity is 105L/L at most, and the purification material has a high purification effect and a long service life; and the compression strength of the purification material is 5.4MPa at most, and the purification material has higher pressure loss resistance.
Description
Technical Field
The application relates to the field of waste gas adsorption, in particular to a high-efficiency purifying material for waste gas containing hydride, a preparation method and application thereof.
Background
The hydride waste gas mainly comprises waste gases of arsine, phosphine, silane, germanium tetrahydride and the like. In the semiconductor industry, a specific amount of impurity source is usually doped into the surface layer of a silicon crystal or other semiconductor crystal to change the electrical characteristics of the semiconductor, and the impurity source is mainly a special gas such as phosphorus, boron, arsenic, etc., so that in the doping process, a large amount of waste gas such as arsine, etc. is generated. The waste gases of arsenic, phosphane and the like are extremely toxic and inflammable gases, and have great harm to the environment and human health.
In the related art, in order to reduce the harm caused by the hydride waste gas such as arsine and phosphine, the special gas which does not participate in the reaction is firstly purified and pretreated by a POU device attached to a clean room and then discharged into a central processing system. The central processing system usually adopts a wet spraying method for waste gases such as arsenic, phosphorus and the like, and the method has low removal rate of arsenic hydride and is easy to generate secondary pollution of waste water. In order to improve the removal rate of arsine, a dry adsorption system is further adopted, and the purification effect on the hydride-containing waste gas is still poor.
Disclosure of Invention
In order to improve the purification effect of the purification material for purifying the waste gas containing the hydride, the application provides a high-efficiency purification material for the waste gas containing the hydride, and a preparation method and application thereof.
In a first aspect, the present application provides a method for preparing a high-efficiency purification material for waste gas containing hydride, which adopts the following technical scheme:
a preparation method of a material for efficiently purifying hydride-containing waste gas comprises the following operation steps:
s1, preparing a carrier;
s2, preparing a copper salt solution with the mass concentration of 60-80%, soaking the carrier in the copper salt solution for 2.5-3.5h, and drying at the temperature of 50-70 ℃ for 4.5-5.5h to obtain a mixture A;
s3, preparing an alkali solution with the molar concentration of 1-1.5mol/L, uniformly stirring, soaking the obtained mixture A in the alkali solution for 2.5-3.5h, and drying at 50-70 ℃ for 2.5-3.5h to obtain the purification material.
In the application, the copper salt solution can be one of a copper nitrate solution, a copper sulfate solution and a copper chloride solution; the alkali solution can be one of sodium hydroxide solution, potassium hydroxide solution, tetramethylammonium hydroxide solution and tetraethylammonium hydroxide solution, when the purifying material is prepared from copper nitrate solution, copper sulfate solution and copper chloride solution, and the alkali solution can be sodium hydroxide solution, potassium hydroxide solution, tetramethylammonium hydroxide solution and tetraethylammonium hydroxide solution, the concentration of the copper salt solution is 60%, 70% and 80%, the molar concentration of the alkali solution is 1mol/L, 1.2mol/L and 1.5mol/L, and the purifying effect of the purifying material is good.
By adopting the technical scheme, the copper nitrate is dissolved in water and hydrolyzed to generate copper ions, the copper ions and hydroxide ions can generate water-insoluble copper hydroxide, the carrier loaded copper ions are added, the first drying can improve the loading performance of the copper ions on the carrier, the temperature is controlled to be 50-60 ℃, the temperature cannot be too high, the copper nitrate is prevented from being decomposed into copper oxide, then the carrier loaded with the copper nitrate is immersed in alkaline solution for alkalization, and the carrier loaded with the copper hydroxide is dried to obtain the copper hydroxide-loaded purification material. The concentration of the sodium hydroxide solution is adjusted, so that the over-high concentration of the sodium hydroxide can be prevented, and the dissolution of copper hydroxide is avoided.
The purification effect of copper hydroxide is higher than that of copper oxide, and the copper hydroxide can be decomposed at high temperature to generate copper oxide, so that the whole preparation method does not adopt high-temperature roasting. And drying the carrier loaded with copper ions at the low temperature of 50-70 ℃ for 4.5-5.5 hours in the step S2 to prevent the copper nitrate from being decomposed into copper oxide under the heating condition and simultaneously enable the copper ions to be better attached to the supporting material, and drying the sodium hydroxide solution impregnated with the mixture A at the low temperature of 50-70 ℃ in the step S3 without high-temperature roasting to prevent the copper hydroxide from being decomposed into copper oxide under the heating condition.
The whole preparation method has the advantages of less types and dosages of used chemical reagents, simple preparation process, easy operation, no need of high-temperature roasting, and reservation of chemical compositions of active components. Therefore, the adsorption effect of the purification material on the arsenic hydride is improved, and the production cost is reduced.
In addition, the specific method for preparing the alumina particle carrier comprises the following steps: adding corn starch and citric acid into water, pulping at 80-100 deg.C, adding activated alumina and cellulose, mixing, co-extruding into granule, drying, and roasting at 550-650 deg.C for 3-5 hr to obtain alumina granule carrier.
Further, the specific method for preparing the macroporous alumina carrier comprises the following steps: adding corn starch and citric acid into water, pulping at 80-100 deg.C, adding macroporous alumina and cellulose, mixing, co-extruding into granule, strip, clover or clover, drying, and roasting at 550-650 deg.C for 3-5 hr to obtain macroporous alumina carrier.
Further, the specific method for preparing the mesoporous alumina carrier comprises the following steps: adding corn starch and citric acid into water, pulping at 80-100 deg.C, adding mesoporous alumina and cellulose, mixing, co-extruding into granule, strip, clover or clover, drying, and roasting at 550-650 deg.C for 3-5 hr to obtain mesoporous alumina carrier.
Preferably, the method comprises the following steps: the mixing amount of the carrier is 50-105% of that of the copper nitrate.
By adopting the technical scheme, the doping amount of the carrier is adjusted, so that the loading of the copper hydroxide is facilitated, the carrying capacity is insufficient due to too small dosage, and the adsorption efficiency of the carrier is influenced due to too high dosage.
Preferably, the method comprises the following steps: the carrier is at least one of alumina carrier, zeolite molecular sieve, diatomite, attapulgite, silica gel powder and active carbon particles.
By adopting the technical scheme, the aluminum oxide is used as the carrier of the copper hydroxide, and the copper hydroxide carrier has the advantages of large specific surface area, porosity, high dispersibility, high-temperature thermal stability and the like. The aluminum oxide has higher adsorption capacity to the arsine, and mainly adsorbs the arsine on the surface of the aluminum oxide. The activated carbon particles have a developed pore structure, good adsorption performance, high mechanical strength and large specific surface area, and are beneficial to fully contacting with waste gases such as arsine and the like to purify the waste gases of the arsine. The zeolite molecular sieve has smaller pore size, so that the zeolite molecular sieve has stronger gravitational field and higher adsorption performance. The silica gel powder is a porous structure with a large specific surface area.
Preferably, the method comprises the following steps: the alumina carrier is active alumina, macroporous alumina, mesoporous alumina and microporous alumina.
By adopting the technical scheme, the shape of the holes formed by the alumina is regular, the support body is easy to be integrally homogenized, and the support body has good compression molding and sintering characteristics. The clover alumina has higher compressive strength, diffusion rate and reactivity.
Preferably, the method comprises the following steps: and when the carrier is prepared in the step S1, extruding and molding the carrier into granules, strips, clover shapes or clover shapes.
The purification material obtained by extruding and molding the carrier into a granular shape, a strip shape or a clover shape has higher purification effect, the removal rate of arsenic hydride is more than 99 percent, and the saturated adsorption capacity is more than 100L/L; in addition, the compressive strength of the carrier is extruded and molded into granules, strips or clover shapes, so that the compressive strength of the obtained purification material is more than 4.3MPa, and the purification material has certain compressive loss resistance.
By adopting the technical scheme, the purification materials with different appearance structures can be obtained, and the purification material with the optimal appearance structure can be selected according to the working condition in the actual arsenic hydride waste gas treatment process.
In a second aspect, the present application provides a purification material obtained by any one of the above methods for producing a high-efficiency purification material for an exhaust gas containing a hydride.
By adopting the technical scheme, the active phase of the obtained purifying material contains copper hydroxide, the activated energy of the purifying material is utilized to carry out chemical adsorption to a greater extent, and the effect of the chemical adsorption is better than that of the physical adsorption, so that the chemical adsorption is mainly utilized along with certain physical adsorption.
In a third aspect, the present application provides a use of any one of the above purification materials in a dry adsorption system for use in treating arsine.
Preferably, the method comprises the following steps: the dry adsorption system comprises an adsorption tower packed with the purification material of claim 6.
Through adopting above-mentioned technical scheme, pack purifying material to the adsorption tower in, be provided with the switch board on the adsorption tower, and be provided with the indicator in the adsorption tower export and look at, be convenient for observe export arsine concentration, purifying material's saturation condition, still be provided with the outlet at the adsorption tower bottom, the moisture in the adsorption tower of being convenient for discharge improves purifying material's adsorption effect.
And a nitrogen protection system is arranged in the dry type adsorption system, and the nitrogen protection system introduces nitrogen into the adsorption tower for purging, so that the safety of operation and equipment is ensured.
In addition, the dry-type adsorption system applied to the application does not need heating, pressurizing and electrolysis in the process of adsorbing arsenic hydride, can be carried out at normal temperature, does not generate secondary pollutants in wastewater, and is simple and convenient to operate due to the automatic control system in the whole process.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) According to the method, the preparation method of the purifying material is adjusted, a drying method is adopted to replace calcination, copper hydroxide is effectively prevented from being reduced into copper oxide, and different types of alumina carriers are selected for test, so that the highest removal rate of the purifying material to arsenic hydride is 100%, and the purifying material has a high purifying effect. In addition, the compressive strength of the purification material is 4.7MPa, and the purification material has higher pressure loss resistance.
(2) According to the method, the alumina carrier is replaced by the zeolite molecular sieve, the silica gel powder, the activated carbon particles, the diatomite and the attapulgite, and the purifying effect of the zeolite molecular sieve, the silica gel powder and the activated carbon particles is lower than that of the alumina particles serving as the carrier.
(3) When the carrier is prepared, the carrier is extruded into a granular shape, a clover shape or a clover shape and then loaded with copper ions, so that the removal rate of the purifying material to the arsine is 100 percent, the compressive strength is 5.1MPa, and the compressive damage resistance of the purifying material is further improved.
(4) By adjusting the doping amount of the carrier, the removal rate of the purification material to the arsenic hydride is 100%, the compressive strength is 5.4MPa, and the compressive damage resistance of the purification material is improved under the condition of not reducing the removal rate.
(5) The preparation method of the purifying material has the advantages of less types and dosage of chemical reagents, simple preparation process, easy operation and no need of high-temperature roasting, improves the adsorption effect of the purifying material on the arsenic hydride, and reduces the production cost.
Drawings
FIG. 1 is an electron microscope scanning image of a mesoporous clover alumina carrier;
FIG. 2 is an electron microscope scanning image of the mesoporous clover alumina carrier after loading.
Detailed Description
The present application will be described in further detail with reference to specific embodiments and drawings.
The following raw materials are all commercially available products, and are not to be construed as limiting the sources of the raw materials, as they are fully disclosed in the present application. The method specifically comprises the following steps: activated alumina with a pore diameter of 5-6mm; macroporous alumina with pore diameter of 14-25nm; mesoporous alumina with a pore diameter of 5-6nm; small pore alumina with pore diameter of 1.5-2nm; the zeolite molecular sieve is ZMS-5,Y type, and the grain diameter is 1.2-1.9mm; silica gel powder with the grain diameter of 1000 meshes; active carbon particles with the particle size of 200 meshes; diatomite with a particle size of 200 meshes; the particle size of the attapulgite is 200 meshes.
Example 1
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 1 comprises the following operation steps:
s1, preparing an alumina particle carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding alumina and cellulose, mixing uniformly, co-extruding into granules, drying, and roasting at 600 ℃ for 4h to obtain the alumina granular carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of alumina particle carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 2
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 2 comprises the following operation steps:
s1, preparing a mesoporous alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding mesoporous alumina and cellulose, uniformly mixing, co-extruding into particles, drying, and roasting at 600 ℃ for 4 hours to obtain the mesoporous alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of mesoporous alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 3
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 3, comprising the following operational steps:
s1, preparing a macroporous alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding macroporous alumina and cellulose, uniformly mixing, co-extruding into particles, drying, and roasting at 600 ℃ for 4 hours to obtain the macroporous alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of macroporous alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 4
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 4, which comprises the following operation steps:
s1, preparing a small-pore alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding the microporous alumina and cellulose, uniformly mixing, co-extruding into particles, drying, and roasting at 600 ℃ for 4 hours to obtain the microporous alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of a small-pore alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 5
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 5, which comprises the following steps:
s1, dissolving 10.5g of copper nitrate in 4.5mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of zeolite molecular sieve in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s2, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 6
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 6, which comprises the following operation steps:
s1, dissolving 12g of copper nitrate in 3mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of silica gel powder in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s2, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 7
The preparation method of the material for high-efficiency purification of hydride-containing exhaust gas of example 7, which comprises the following operation steps:
s1, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of activated carbon particles in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s2, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 8
The production method of the material for high-efficiency purification of hydride-containing exhaust gas of example 8, which comprises the following operational steps:
s1, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of kieselguhr in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s2, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 9
The production method of the material for high-efficiency purification of hydride-containing exhaust gas of example 9, which comprises the following operational steps:
s1, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of attapulgite in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s2, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 10
The preparation process of a material for high-efficiency purification of hydride-containing exhaust gas of example 10, which comprises the following steps:
s1, preparing a mesoporous clover alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding mesoporous alumina and cellulose, uniformly mixing, co-extruding into clover shape, drying, and roasting at 600 ℃ for 4 hours to obtain the mesoporous clover alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of mesoporous clover alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 11
The production method for a high-efficiency purification material for hydride-containing exhaust gas of example 11, which comprises the following operational steps:
s1, preparing a mesoporous clover alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding mesoporous alumina and cellulose, uniformly mixing, co-extruding into clover shape, drying, and roasting at 600 ℃ for 4 hours to obtain the mesoporous clover alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 6.75g of mesoporous clover alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 12
The production method for a high-efficiency purification material for hydride-containing exhaust gas of example 12, which comprises the following operational steps:
s1, preparing a mesoporous clover alumina carrier: adding corn starch and citric acid into water, pulping at 90 deg.C, adding mesoporous alumina and cellulose, mixing, co-extruding into clover shape, drying, and roasting at 600 deg.C for 4 hr to obtain mesoporous clover alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 7.5g of mesoporous clover alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
and S3, preparing a 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3 hours, and drying at 60 ℃ for 3 hours to obtain the purification material.
Example 13
The production method for a high-efficiency purification material for hydride-containing exhaust gas of example 13, which comprises the following operational steps:
s1, preparing a mesoporous clover alumina carrier: adding corn starch and citric acid into water, pulping at 90 ℃, adding mesoporous alumina and cellulose, uniformly mixing, co-extruding into clover shape, drying, and roasting at 600 ℃ for 4 hours to obtain the mesoporous clover alumina carrier.
S2, dissolving 9g of copper nitrate in 6mL of water, uniformly stirring to obtain a copper salt solution, soaking 16.5g of mesoporous clover alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purification material.
Example 14
The preparation process for a high-efficiency purification material for hydride-containing exhaust gas of example 14, which comprises the following operational steps:
s1, preparing a mesoporous clover alumina carrier (shown in a figure 1): adding corn starch and citric acid into water, pulping at 90 deg.C, adding mesoporous alumina and cellulose, mixing, co-extruding into clover shape, drying, and roasting at 600 deg.C for 4 hr to obtain mesoporous clover alumina carrier.
S2, dissolving 10g of copper nitrate in 4.28mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of mesoporous clover alumina carrier in the copper salt solution for 3 hours, and drying at 60 ℃ for 5 hours to obtain a mixture A;
and S3, preparing a 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and drying at 60 ℃ for 3h to obtain the purifying material (shown in figure 2).
Comparative example 1
The preparation method of the material for highly efficient purification of hydride-containing exhaust gas of comparative example 1 comprises the following operation steps:
s1, preparing an alumina particle carrier: the same as in example 1.
S2, dissolving 9g of copper nitrate in 9mL of water, uniformly stirring to obtain a copper salt solution, soaking 15.75g of alumina carrier in the copper salt solution for 3 hours, and roasting at 450 ℃ for 5 hours to obtain a mixture A;
s3, preparing 1mol/L sodium hydroxide aqueous solution, uniformly stirring, soaking the obtained mixture A in the sodium hydroxide aqueous solution for 3h, and roasting at 450 ℃ for 5h to obtain the purification material.
Comparative example 2
The preparation method of the material for highly efficient purification of hydride-containing exhaust gas of comparative example 2 comprises the following operation steps: mixing 45g of copper hydroxide, 5g of soda lime, 45g of alumina powder, 3g of silica sol and 2g of aluminum sol, uniformly stirring, extruding into a clover shape, drying at 50 ℃ for 24h, and calcining at 400 ℃ for 10h to obtain the purification material.
Comparative example 3
The preparation method of the material for highly efficient purification of hydride-containing exhaust gas of comparative example 3 comprises the following operation steps: mixing 45g of copper hydroxide, 5g of soda lime, 45g of alumina powder, 3g of silica sol and 2g of aluminum sol, uniformly stirring, extruding into a clover shape, and drying for 24h at 50 ℃ to obtain the purification material.
Comparative example 4
The preparation method of the material for highly efficient purification of hydride-containing exhaust gas of comparative example 4 comprises the following operation steps: mixing 45g of copper nitrate, 5g of soda lime, 45g of alumina powder, 3g of silica sol and 2g of aluminum sol, uniformly stirring, extruding into a clover shape, and calcining for 10 hours at 400 ℃ to obtain the purification material.
Comparative example 5
The preparation method of the material for highly efficient purification of hydride-containing exhaust gas of comparative example 5 comprises the following operation steps: mixing 45g of copper nitrate, 5g of soda lime, 45g of alumina powder, 3g of silica sol and 2g of aluminum sol, uniformly stirring, extruding into a clover shape, and drying for 24 hours at 50 ℃ to obtain the purification material.
Performance detection
The following methods were used to measure the specific surface area, pore volume and average particle size of the purification materials obtained in examples 1-10, and the results are shown in Table 1, and the results are shown in Table 2.
Specific surface area: the specific surface area of the purification material was measured by the BET volumetric method.
Pore volume: and (3) measuring the pore volume of the purifying material by adopting a BET low-temperature nitrogen adsorption method.
Average pore diameter: the average pore size of the purification material is determined by a BET low temperature nitrogen adsorption method.
Compressive strength: the WE-100 type hydraulic universal tester tests the pressure of the purification material during crushing, and the compressive strength of the purification material is calculated according to the surface area of the stress surface.
Adsorption performance: the purification materials obtained in examples 1 to 14 and comparative examples 1 to 5 were charged into a reactor, and the concentration of arsine was set to 1ppm and the test space velocity was 6114h -1 The removal rate of arsine of each purification material was measured.
Saturated adsorption capacity: the saturated adsorption capacity of the purification material was measured using an isothermal adsorption line.
TABLE 1 Performance test results for different purification materials
TABLE 2 Performance test results for different purification materials
The detection results in Table 1 show that the pore volume of the purifying material obtained by the method is up to 1.26m 3 (ii)/g; the detection results in table 2 show that the purification material obtained by the method has the highest removal rate of 100% of arsine and has a high purification effect; the compression strength of the purification material is 5.4MPa at most, and the purification material has higher pressure loss resistance; and the maximum saturated adsorption capacity is 105L/L, the purification material filled in the adsorption tower can be replaced once in 2-3 years, and the service life of the purification material is prolonged.
The detection results in Table 2 show that in examples 1-4, the removal rate of arsine by the purification material of example 2 is 100%, which is higher than that in examples 1 and 3-4, and that the purification effect is higher than that of the active alumina carrier, the macroporous alumina carrier and the microporous alumina carrier when the carrier is mesoporous alumina, and the compressive strength is 4.7MPa, which is higher than that in examples 1 and 3-4, so that the purification material has higher compressive loss resistance.
The performance test data of the purifying materials in the embodiment 2 and the embodiments 5 to 9 are combined to find that the removing rate of the purifying material in the embodiment 2 to the arsine is 100 percent, which is higher than that in the embodiments 5 to 9, and shows that the purifying effect of the carrier of the zeolite molecular sieve, the silica gel powder, the activated carbon particles, the diatomite and the attapulgite is lower than that of the carrier of the alumina.
The performance test data of the purification materials of the embodiment 2 and the embodiment 10 show that the compression strength of the purification material of the embodiment 10 to the arsine is 5.1MPa, which is higher than that of the embodiment 2, and the compression effect of the carrier extruded into a clover shape is higher than that of the granular purification material.
In examples 11 to 14, the removal rate of arsine by the purification materials of examples 12 and 14 was 100% higher than that of examples 11 and 13, indicating that the adsorption effect of the purification materials on arsine was higher when the loading of the carrier was 50 to 105% of that of copper nitrate. In addition, the compressive strength of the purification material of example 14 is 5.4MPa, which is higher than that of examples 11-13, indicating that the anti-compression performance of the purification material is greatly influenced by the addition amount of the carrier in the purification material.
In addition, the combination of the index data of the purification materials of comparative examples 1-5 and example 1 shows that the purification material of the present application can improve the adsorption effect of the purification material on arsine by directly drying at a low temperature of 60 ℃ without calcining in the preparation process, and the purification effect of directly preparing copper hydroxide or copper nitrate into the purification material is lower than that of the method for preparing and precipitating the copper salt solution.
The following are examples of applications of the purification material
The purification material prepared by the method is filled into a dry adsorption system for treating arsine in the pan-semiconductor industry, wherein the dry adsorption system comprises an adsorption tower, a control cabinet and a nitrogen protection system.
The purifying material is filled into the adsorption tower, the adsorption tower is provided with a control cabinet and a nitrogen protection system, the gas pressure, the gas concentration at the outlet and the temperature in the adsorption tower are measured by the programmable logic controller for installing the control cabinet, and specific measurement data are displayed through a human-computer interface. And the pressure sensor, the outlet concentration detector and the temperature detector on the adsorption tower are set with safe values, and any value exceeds the limit, so that the alarm can be started.
The nitrogen protection system can be used for blowing dust attached to the inner surface of the tower by using high-pressure nitrogen during the shutdown maintenance or the replacement of the adsorbent in the actual treatment process, the valve of the nitrogen is in chain reaction with the outlet temperature, the nitrogen is opened when the outlet temperature is higher than a set value, and the nitrogen is introduced for cooling, so that the adsorption efficiency of the waste gas containing the arsenic hydride is improved, and when the system is abnormal, the nitrogen is used for blowing away the gas in the adsorption tower, so that the increase of the concentration of the arsenic hydride can be effectively prevented.
Application example 1
Application example 1 the application method of the purification material is as follows: the purification material obtained in example 2 was packed to a capacity of 1.5m 3 The loading in the adsorption column was 1.2 ton, the feed gas concentration of arsine was 0.01ppm, and the temperature in the adsorption column was controlled to 23 ℃ and the relative humidity was 45%.
Application examples 2 to 4
Application examples 2 to 4 were the same as application example 1 except that the purification materials of example 10, example 12 and example 14 were used in application examples 2 to 4, respectively.
Performance detection
The following methods were used to test the performance of the purified materials obtained in the different application examples 1-4, and the test results are shown in Table 3.
Removal rate of arsine gas: and detecting the content of the arsenic hydride in the waste gas before and after treatment, and calculating the removal rate of the purifying material on the arsenic hydride.
TABLE 3 Performance test results with decontaminant materials
The results of the tests in Table 3 show that the highest removal rate of arsine can be 100% when the waste gas containing arsine generated by the generic semiconductor is actually treated, and the purification effect of the purification material is improved.
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 (3)
1. Use of a purification material for the treatment of arsine, said purification material being obtainable by the following steps:
s1, preparing a carrier;
s2, preparing a copper salt solution with the mass concentration of 60-80%, soaking a carrier with the doping amount of 50-105% of the copper salt solution in the copper salt solution for 2.5-3.5h, and drying at 50-70 ℃ for 4.5-5.5h to obtain a mixture A;
s3, preparing an alkali solution with the molar concentration of 1-1.5mol/L, uniformly stirring, soaking the obtained mixture A in the alkali solution for 2.5-3.5h, and drying at 50-70 ℃ for 2.5-3.5h to obtain a purification material;
the carrier is an alumina carrier; the alumina carrier is mesoporous alumina; and when the carrier is prepared in the step S1, extruding and molding the carrier into a clover shape.
2. Use according to claim 1, characterized in that: the purification material employs a dry adsorption system in the treatment of arsine.
3. Use according to claim 2, characterized in that: the dry adsorption system comprises an adsorption tower packed with the purification material of claim 1.
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