CN114073945B - Composite alumina catalyst and preparation method and application thereof - Google Patents
Composite alumina catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 42
- 239000000126 substance Substances 0.000 abstract description 7
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910001679 gibbsite Inorganic materials 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/615—
-
- B01J35/647—
-
- B01J35/69—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a composite alumina catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts. The preparation method of the composite alumina catalyst comprises the following steps: X-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 Soaking the mixture in alkali solution, and stirring uniformly; filtering the uniformly stirred mixed solution to obtain a filtered mixture; and washing and drying the filtered mixture, and roasting to obtain the composite alumina catalyst. The catalyst has a large specific surface area and an open pore canal structure, pore diameters are distributed in a double-peak mode, and the catalyst also has unique surface chemical properties. When the catalyst is used in the Claus reaction, SO can be promoted 2 And H is 2 Synchronous conversion of S with higherIs active and has a longer service life. The preparation method is simple and easy to operate, low in cost and convenient for large-scale popularization and utilization.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite alumina catalyst and a preparation method and application thereof.
Background
In industries such as oil refining, natural gas purification, coal chemical industry and the like, sulfur recovery is generally performed by using a sulfur recovery device, and during operation, a combustion furnace in the sulfur recovery device inevitably generates CS 2 And COS, and the like. Most of the organic sulfur will be hydrolyzed by the catalyst in the claus reactor, and the unhydrolyzed organic sulfur will enter the burning furnace and finally be used as SO 2 The form is vented to atmosphere through a chimney. Therefore, in order to reduce the SO in the tail gas 2 The amount of the discharged organic sulfur is required to increase the hydrolysis rate of the organic sulfur.
In the related art, the catalyst for the hydrolysis of organic sulfur includes gamma-Al 2 O 3 A catalyst, wherein the gamma-Al 2 O 3 The abundance of pores in the catalyst provides a very high specific surface area, which is beneficial for the claus reaction activity (wherein claus reaction activity refers to the reaction of H when the catalyst is subjected to a claus reaction) 2 S and SO 2 Is advantageous in terms of conversion).
In carrying out the invention, the present inventors have found that there are at least the following problems in the prior art:
γ-Al 2 O 3 the catalyst is easily blocked by capillary condensed sulfur, and sulfur generated in the pore cavity is difficult to diffuse outwards due to the narrow pore opening, and the Claus reaction activity is also reduced.
Disclosure of Invention
In view of the above, the invention provides a composite alumina catalyst, a preparation method and application thereof, and the composite alumina catalyst has higher Claus reaction activity.
Specifically, the method comprises the following technical scheme:
in one aspect, a method for preparing a composite alumina catalyst is provided, the method for preparing the composite alumina catalyst comprising: X-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 Soaking the mixture in alkali solution, and stirring uniformly;
filtering the uniformly stirred mixed solution to obtain a filtered mixture;
and washing and drying the filtering mixture, and roasting to obtain the composite alumina catalyst.
In some possible implementations, the χ -Al 2 O 3 The particles have a size of less than or equal to 50 microns.
In some possible implementations, the χ -Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The weight ratio of (2) is 1:1-10.
In some possible implementations, the χ -Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The soaking time of the mixture in the alkaline solution is 2-24 hours, and the mass concentration of the alkaline solution is 0.5% -10%.
In some possible implementations, a microwave drying mode is adopted when the drying is performed, and the time of microwave drying is 2-30 minutes.
In some possible implementations, the firing is performed at a rate of 3 ℃/min to 15 ℃/min.
In some possible implementations, the final firing temperature is 450 ℃ to 500 ℃ and the incubation time at the final firing temperature is 2 to 24 hours when the firing is performed.
In another aspect, a composite alumina catalyst is provided, the composite alumina catalyst is prepared by any one of the preparation methods, and the composite alumina catalyst comprises: X-Al 2 O 3 And gamma-Al 2 O 3 。
In a further aspect, there is provided the use of the composite alumina catalyst described above in a claus reaction process.
In some possible implementations, the application includes: SO as to contain SO2 and H 2 S and N 2 Introducing the mixture into a fixed bed reactor filled with the composite alumina catalyst to perform the claus reaction.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the preparation method of the composite alumina catalyst provided by the embodiment of the invention can be used for preparing catalyst containing X-Al 2 O 3 And gamma-Al 2 O 3 Wherein, X-Al is used as the composite alumina catalyst 2 O 3 Particle and cluster gamma-Al 2 O 3 As a preparation raw material, the alumina is soaked in alkali solution and stirred uniformly to change the acid and alkali properties of the surfaces of the alumina particles, and simultaneously, the alumina is subjected to alkali etching. Filtering the uniformly stirred mixed solution to remove liquid in the mixed solution, thereby obtaining a filtering mixture; the filtered mixture is washed to remove impurities, and then sequentially dried and calcined to obtain the composite alumina catalyst. The composite alumina catalyst is coupled with X-Al 2 O 3 And gamma-Al 2 O 3 The structure and the performance of the porous polymer not only have larger specific surface area and open pore canal structure, but also have unique surface chemical properties, and the pore diameter is in bimodal distribution. When the composite alumina catalyst is used in the Claus reaction, SO can be effectively promoted 2 And H is 2 S has higher Claus reaction activity and longer service life. In addition, the preparation method of the composite alumina catalyst provided by the embodiment of the invention is simple and easy to operate, and the X-Al 2 O 3 Low cost and convenient large-scale popularization and utilization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation method of a composite alumina catalyst provided by an embodiment of the invention.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
The inventors have made a reaction to Al 2 O 3 Materials have been studied, in particular for χ -Al 2 O 3 And clustered gamma-Al 2 O 3 Research has been conducted in which clustered gamma-Al 2 O 3 The one-dimensional or two-dimensional secondary structural units are bound together in a certain way (such as around a certain point in space or along a certain line in space) through interaction to form a special three-dimensional structure, namely, the three-dimensional structure has a nano-scale structural unit and an overall morphology of a micron and above scale, and can generate coupling and synergistic effects on a micro-nano scale, so that the material has a certain specific surface area, and meanwhile, has an open pore structure, and has a large average pore diameter, thereby being very beneficial to the diffusion of substances. However, clustered gamma-Al 2 O 3 Not currently used in the claus reaction process.
High purity χ -Al 2 O 3 Has important significance for industrial application and influences X-Al 2 O 3 The main factor of the purity is that the aluminum hydroxide used as the raw material is heated in the heating processIs equivalent to the dehydration and phase inversion rate of the catalyst to obtain high-purity X-Al 2 O 3 。
The embodiment of the invention provides a preparation method of a composite alumina catalyst, which is shown in a figure 1, and comprises the following steps:
The preparation method of the composite alumina catalyst provided by the embodiment of the invention can be used for preparing catalyst containing X-Al 2 O 3 And gamma-Al 2 O 3 Wherein, X-Al is used as the composite alumina catalyst 2 O 3 Particle and cluster gamma-Al 2 O 3 As a preparation raw material, the alumina is soaked in alkali solution and stirred uniformly to change the acid and alkali properties of the surfaces of the alumina particles, and simultaneously, the alumina is subjected to alkali etching. Filtering the uniformly stirred mixed solution to remove liquid in the mixed solution, thereby obtaining a filtering mixture; the filtered mixture is washed to remove impurities, and then sequentially dried and calcined to obtain the composite alumina catalyst. The composite alumina catalyst is coupled with X-Al 2 O 3 And gamma-Al 2 O 3 The structure and the performance of the porous polymer not only have larger specific surface area and open pore canal structure, but also have unique surface chemical properties, and the pore diameter is in bimodal distribution. When the composite alumina catalyst is used in the Claus reaction, SO can be effectively promoted 2 And H is 2 S has higher Claus reaction activity and longer service life. In addition, the preparation method of the composite alumina catalyst provided by the embodiment of the invention is simple and easy to operate, and the X-Al 2 O 3 Low cost and convenient large-scale popularization and utilization.
Wherein, the pore diameter of the composite alumina catalyst is in a bimodal distribution, and the pore diameter of the composite alumina catalyst comprises two distribution ranges, wherein one part is in a small pore diameter range, such as 3nm-5nm, and the other part is in a medium pore diameter range, such as 25nm-35nm.
The composite alumina catalyst prepared by the embodiment of the invention has unique surface chemical property, namely, the composite alumina catalyst has better adsorptivity and activation for hydrogen sulfide and sulfur dioxide, thereby being suitable for the reaction of the hydrogen sulfide and the sulfur dioxide.
The following describes the steps involved in the preparation method of the composite alumina catalyst provided in the embodiment of the present invention:
for step 101, X-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 Soaking in alkali solution, and stirring.
Wherein, soaking the X-Al with alkali solution 2 O 3 Particle and cluster gamma-Al 2 O 3 Can change the acid-base property of the surface of the alumina particles and simultaneously make the alumina undergo the alkali etching action so as to enhance the specific surface area of the alumina.
To improve X-Al 2 O 3 Dispersibility of particles, in the examples of the present invention, χ -Al 2 O 3 The particles have a size of less than or equal to 50 microns, for example from 5 microns to 50 microns.
For example, in the embodiment of the present invention, χ -Al 2 O 3 Particle sizes of the particles include, but are not limited to: 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, etc.
In the embodiment of the invention, the high-purity X-Al 2 O 3 The particles can be prepared by the following preparation method:
step 201, soaking alpha-gibbsite particles with the granularity of 10 micrometers-100 micrometers in an alcohol aqueous solution to obtain a mixed solution.
Wherein the alcohol is at least one selected from methanol, ethanol, n-propanol, isopropanol and ethylene glycol; the ratio of the volume of the aqueous solution of the alcohol to the bulk volume of the alpha-gibbsite particles is 0.5-2:1; the soaking time of the alpha-gibbsite particles in the aqueous solution of the alcohol is 2-24 hours.
And 202, performing hydrothermal treatment on the mixed solution by using a hydrothermal reaction kettle, and then filtering and draining to obtain a drained sample.
Wherein the temperature of the hydrothermal treatment is 100-200 ℃, and the time of the hydrothermal treatment is 1-24 hours.
And 203, placing the drained sample into a drying box, and introducing nitrogen for drying to obtain a dried sample.
Wherein, the temperature of the drained sample is 200-300 ℃ and the drying time is 2-24 hours; the flow rate of the nitrogen is 5mL/min-50mL/min.
And 204, placing the dried sample into a tube furnace for roasting, and cooling to obtain the catalyst for hydrolyzing the organic sulfur.
Wherein, when roasting, the heating rate is 0.1 ℃/min-3 ℃/min, the roasting final temperature is 400 ℃ to 700 ℃ and the final temperature holding time is 2 to 24 hours.
The preparation method takes alpha-gibbsite particles as a preparation raw material, and the alpha-gibbsite particles are soaked in an aqueous solution of alcohol to be fully dispersed. The mixed solution containing the alpha-gibbsite is subjected to hydrothermal treatment, so that the interaction among the alpha-gibbsite powder particles can be changed, and the shaping can be realized. The sample obtained after the hydrothermal treatment is filtered and drained is dried to remove the moisture in the sample, and finally the sample is roasted to ensure that the alpha-gibbsite is subjected to crystal phase transformation, so that the high-purity X-Al can be obtained 2 O 3 For example, X-Al with a purity of more than 90% 2 O 3 。
In embodiments of the present invention, it is desirable that the χ -Al used 2 O 3 The specific surface area of the particles was 200m 2 /g-300m 2 In this way, a higher specific surface area can be imparted to the composite alumina catalyst.
For example, χ -Al 2 O 3 Specific surface areas of the particles include, but are not limited to: 200m 2 /g、210m 2 /g、220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g、260m 2 /g、270m 2 /g、280m 2 /g、290m 2 /g、300m 2 /g, etc.
Clustered gamma-Al 2 O 3 Is a novel Al with unique morphology 2 O 3 The material is formed by stacking micron-sized clusters formed by blades with the thickness of nanometers and has a flower-like structure, N 2 The adsorption and desorption isotherm is H3 type and has an open pore structure.
In the embodiment of the invention, the clustered gamma-Al is used 2 O 3 Has a specific surface area of 100m 2 /g-250m 2 The crystal phase is gamma type, and the bulk density of the powder is 0.01g/cm 3 -0.10g/cm 3 . The clustered gamma-Al 2 O 3 Can be obtained by commercial or self-made, and clustered gamma-Al 2 O 3 The preparation method can be referred to as a preparation method described in Chinese patent application CN 102718236A.
In the embodiment of the invention, clustered gamma-Al is formed 2 O 3 With χ -Al 2 O 3 The weight ratio of the particles is 1:1-10, further 1:2-5, e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.
By reacting chi-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The weight ratio of (c) is as defined above, further facilitating the composite alumina catalyst having the bimodal pore distribution and unique surface chemistry mentioned above.
In order to obtain better soaking effect, according to the embodiment of the invention, the X-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The soaking time in the alkaline solution is 2 to 24 hours, further 6 to 12 hours, and for example, may be 5 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, etc.
In the embodiment of the invention, the alkali solution used can be sodium hydroxide solution or ammonia water solution, and the alkali concentration in the alkali solution is 0.5% -10%, and further 1% -5%, so that a dilute alkali solution is obtained. Wherein, the mass concentration of the alkali solution is limited up and down, so that the surface property can be well regulated.
χ-Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The ratio of the bulk volume of the mixture to the volume of the alkaline solution was 1:0.5-2:1, further, 0.8-1.2:1. the arrangement is so as to ensure that a better soaking effect is obtained.
For example, the ratio of the volume of the aqueous solution of the alcohol to the bulk volume of the alpha-gibbsite particles includes, but is not limited to: 0.7: 1. 0.8: 1. 0.9:1: 1.1: 1. 1.1: 1. 1.2:1, etc.
For step 102, the uniformly stirred mixed solution is filtered to obtain a filtered mixture. Wherein, the filtration can be performed by adopting a suction filtration mode.
In step 103, the filtered mixture is washed and dried, and then calcined, thereby obtaining a composite alumina catalyst.
Wherein, in the process of washing, the adopted washing liquid is deionized water.
The washed filtered mixture was dried to remove water from the surface thereof. The drying mode can adopt microwave drying, the heat conduction direction of the microwave drying is the same as the water diffusion direction, and compared with the traditional drying mode, the microwave drying has the advantages of high drying rate, energy conservation, high production efficiency, uniform drying, clean production, easy realization of automatic control, product quality improvement and the like.
In the case of the above microwave drying, the time is 2 to 30 minutes, and for example, 5 minutes, 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, and the like can be used.
The temperature of the microwave drying is 90℃to 120℃such as 95℃100℃105℃110 ℃.
And roasting the dried sample, for example, putting the sample into a tube furnace for roasting, and cooling to obtain the expected composite alumina catalyst.
Wherein the composite alumina of the desired crystal form is obtained by calcination. Ventilation treatment is carried out simultaneously during roasting, so that full roasting can be carried out under a certain atmosphere, and further transformation of crystal phases caused by heat accumulation on the surface of the crystal is avoided.
In some possible implementations, the firing is performed at a rate of 2 ℃/min to 15 ℃/min, and further, 5 ℃/min to 10 ℃/min, for example, including but not limited to: 2 ℃/min, 3 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, etc.
At firing, the firing final temperature (i.e., the final temperature after the temperature rise) is 450 ℃ to 500 ℃, for example, including but not limited to: 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, etc.
The final temperature of the roasting is kept for 2-24 hours, and further, the final temperature is kept for 6-12 hours. For example, the final temperature soak time of calcination includes, but is not limited to: 5 hours, 10 hours, 12 hours, 15 hours, 20 hours, 22 hours, 24 hours, etc.
By the last operating parameters in the roasting treatment, the method comprises the following steps: the temperature rising rate, the final temperature of roasting and the final temperature holding time of roasting are defined as above, so that the purity of the composite alumina catalyst is higher, and the composite alumina catalyst is favorable for obtaining a desired crystal form.
On the other hand, the embodiment of the invention also provides a composite alumina catalyst, which is prepared by adopting any one of the preparation methods, and comprises the following steps: X-Al 2 O 3 And gamma-Al 2 O 3 。
The embodiment of the invention provides a composite alumina catalyst which is coupled with X-Al 2 O 3 And gamma-Al 2 O 3 The structure and the performance of the porous polymer not only have larger specific surface area and open pore canal structure, but also have unique surface chemical properties, and the pore diameter is in bimodal distribution. When the composite alumina catalyst is used in the Claus reaction, SO can be effectively promoted 2 And H is 2 S has higher Claus reaction activity and longer service life.
In a further aspect, embodiments of the present invention also provide the use of any of the composite alumina catalysts referred to above in a claus reaction process.
When the composite alumina catalyst described above is used in the course of the claus reaction, a higher claus reaction efficiency can be obtained.
For example, SO may be contained 2 、H 2 S and N 2 Is introduced into a fixed bed reactor filled with a composite alumina catalyst to carry out the claus reaction.
Wherein, in the mixed gas, H 2 The volume fraction of S is 3-5%; SO (SO) 2 The volume fraction of (2) to (4), H 2 The volume fraction of O is 20-30%, and the balance is nitrogen.
In the Claus reaction, the reaction temperature is 200-350 ℃ and the gas space velocity is 800h -1 -5000h -1 Is carried out under the condition of (2).
The invention will be further illustrated with reference to specific examples.
It should be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages, ratios, proportions, or parts are by weight unless otherwise indicated. The units in weight volume percent are well known to those skilled in the art and refer, for example, to the weight of solute in 100 milliliters of solution.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are presented for illustrative purposes only.
Example 1
50g of X-Al with granularity less than 50 microns 2 O 3 Particles with 12g of clustered gamma-Al 2 O 3 The mixture was immersed in 200mL of 5% strength by mass sodium hydroxide solution while mechanically stirring for 10 hours. Filtering the uniformly stirred mixed solutionThe filtered mixture was obtained. Washing the filtering mixture, performing microwave drying for 30 minutes, then placing the mixture in a tube furnace for roasting, and naturally cooling to obtain the composite alumina catalyst.
Wherein, when the roasting is carried out, the heating rate is 8 ℃/min, the roasting final temperature is 500 ℃, and the final temperature holding time is 10 hours.
The prepared composite alumina catalyst is subjected to parameter measurement, and the specific surface area of the catalyst is 253m 2 And/g, the pore diameter is in bimodal distribution, the average pore diameter of small pores is 3.6nm, and the average pore diameter of large pores is 32nm.
The composite catalyst prepared in this example was charged into a fixed bed reactor and introduced with SO-containing catalyst 2 、H 2 S and N 2 Wherein H is 2 S volume fraction 5%, SO 2 Volume fraction of 2.5%, H 2 The volume fraction of O is 25%, the rest is N 2 Gas space velocity of 3000h -1 The claus reaction is carried out at a temperature of 300 ℃.
After 0.5h of the Claus reaction, the gas composition at the outlet of the fixed bed reactor was determined and the Claus conversion was calculated to be 67%. After 10h of the Claus reaction, the gas composition at the outlet of the fixed bed reactor was determined and the Claus conversion was calculated to be 66.7%.
Example 2
50g of X-Al with granularity less than 50 microns 2 O 3 Particles with 8g of clustered gamma-Al 2 O 3 The mixture was immersed in 80mL of an aqueous ammonia solution having a mass concentration of 6% while mechanically stirring for 24 hours. Filtering the uniformly stirred mixed solution to obtain a filtered mixture. Washing the filtering mixture, performing microwave drying for 10 minutes, then placing the mixture in a tube furnace for roasting, and naturally cooling to obtain the composite alumina catalyst.
Wherein, when the roasting is carried out, the heating rate is 19 ℃/min, the roasting final temperature is 490 ℃, and the final temperature holding time is 24 hours.
The prepared composite alumina catalyst is subjected to parameter measurement, and the specific surface area of the catalyst is 264m 2 /g, wellThe diameters are in bimodal distribution, the average pore diameter of the small pores is 3.6nm, and the average pore diameter of the large pores is 31nm.
The composite catalyst prepared in this example was charged into a fixed bed reactor and introduced with SO-containing catalyst 2 、H 2 S and N 2 Wherein H is 2 S volume fraction 5%, SO 2 Volume fraction of 2.5%, H 2 The volume fraction of O is 25%, the rest is N 2 The gas space velocity is 800h -1 The claus reaction is carried out at a temperature of 200 ℃.
After 0.5h of the Claus reaction, the gas composition at the outlet of the fixed bed reactor was determined and the Claus conversion was calculated to be 80%. After 10 hours of the claus reaction, the gas composition at the outlet of the fixed bed reactor was measured, and the claus conversion was calculated to be 78%.
Example 3
50g of X-Al with granularity less than 50 microns 2 O 3 Particles with 50g of clustered gamma-Al 2 O 3 The mixture was immersed in 600mL of 1% strength by mass aqueous ammonia solution while mechanically stirring for 24 hours. Filtering the uniformly stirred mixed solution to obtain a filtered mixture. Washing the filtering mixture, performing microwave drying for 15 minutes, then placing the mixture in a tube furnace for roasting, and naturally cooling to obtain the composite alumina catalyst.
Wherein, when the roasting is carried out, the heating rate is 10 ℃/min, the roasting final temperature is 500 ℃, and the final temperature holding time is 12 hours.
The prepared composite alumina catalyst is subjected to parameter measurement, and the specific surface area of the catalyst is 232m 2 And/g, the pore diameter is in bimodal distribution, the average pore diameter of small pores is 3.6nm, and the average pore diameter of large pores is 32nm.
The composite catalyst prepared in this example was charged into a fixed bed reactor and introduced with SO-containing catalyst 2 、H 2 S and N 2 Wherein H is 2 S volume fraction 5%, SO 2 Volume fraction of 2.5%, H 2 The volume fraction of O is 25%, the rest is N 2 Gas space velocity of 5000h -1 Claus at a temperature of 350 DEG CAnd (3) reacting.
After 0.5h of the Claus reaction, the gas composition at the outlet of the fixed bed reactor was determined and the Claus conversion was calculated to be 55%. After 10h of the Claus reaction, the gas composition at the outlet of the fixed bed reactor was determined and the Claus conversion was calculated to be 54.5%.
Comparative example 1
This comparative example was compared with example 1 using conventional commercial spherical alumina as the catalyst.
Firstly grinding common commercial spherical alumina (purchased from national reagent group) to make the granularity smaller than 50 microns; the specific surface area was found to be 209m 2 And/g, wherein the pore diameter is unimodal, the average pore diameter of small pores is 5.1nm, and no macropore value exists.
The reactor outlet gas composition was measured after 0.5h under the same test conditions as in example 1, and the claus conversion was calculated to be 62%. After 5 hours, the bed layer is blocked, and the reaction is difficult to continue.
Comparative example 2
This comparative example was compared with example 1 using conventional commercial spherical alumina as the catalyst.
Firstly grinding common commercial spherical alumina (purchased from national reagent group) to make the granularity smaller than 50 microns; weighing 62g of the sample, immersing the sample in 200mL of 5% sodium hydroxide dilute solution by weight, and mechanically stirring for 10 hours; filtering and washing the soaked commercial alumina particles, and drying the commercial alumina particles for 2 hours at the temperature of 120 ℃ in a conventional drying oven; then placing the mixture into a tube furnace for ventilation roasting, and keeping the temperature for 10 hours at 500 ℃ at a heating rate of 8 ℃/min. Naturally cooling to obtain the commercial alumina catalyst. Specific surface area was measured to be 223m 2 And/g, wherein the pore diameter is unimodal, the average pore diameter of small pores is 5.0nm, and no macropore value exists.
The reactor outlet gas composition was measured after 0.5h under the same test conditions as in example 1, and calculated to give 65% claus. After 0.5h the bed was blocked and it was difficult to continue the reaction.
Comparative example 3
The comparative example uses high purity χ -Al 2 O 3 Catalyst was prepared alone and compared with example 1。
Firstly grinding X-Al 2 O 3 Particles having a particle size of less than 50 microns; weigh 62g of X-Al 2 O 3 Soaking in 200mL of 5% sodium hydroxide dilute solution by weight concentration, and mechanically stirring for 10 hours; soaking the soaked X-Al 2 O 3 Filtering, washing and microwave drying the particles for 30 minutes; draining the drained X-Al 2 O 3 The granules are put into a tube furnace for ventilation roasting, the heating rate is 8 ℃/min, and the temperature is kept at 500 ℃ for 10 hours. Naturally cooling to obtain X-Al 2 O 3 A catalyst. The specific surface area was found to be 271m 2 And/g, wherein the pore diameter is unimodal, the average pore diameter of small pores is 3.6nm, and no macropore value exists.
The reactor outlet gas composition was measured after 0.5h under the same test conditions as in example 1, and the claus conversion was calculated to be 68%. After 1h, the bed was blocked, and it was difficult to continue the reaction.
The foregoing description is only for the convenience of those skilled in the art to understand the technical solution of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method of preparing a composite alumina catalyst for use in a claus reaction, the method comprising: mixing the chi-Al with purity of more than 90 percent 2 O 3 Particle and cluster gamma-Al 2 O 3 Soaking the mixture in alkali solution, and stirring uniformly;
filtering the uniformly stirred mixed solution to obtain a filtered mixture;
washing and drying the filtering mixture, and roasting to obtain the composite alumina catalyst;
the clustered gamma-Al 2 O 3 With said X-Al 2 O 3 The weight ratio of the particles is 1:2-5;
the X-Al 2 O 3 Particles and the clustered gamma-Al 2 O 3 The ratio of the bulk volume of the mixture to the volume of the alkaline solution is 1:0.5-2:1, a step of;
the alkali solution is sodium hydroxide solution or ammonia water solution, and the mass concentration of the alkali solution is 0.5% -10%;
the Claus reaction is carried out by reacting a catalyst containing SO 2 、H 2 S and N 2 Is introduced into a fixed bed reactor filled with the composite alumina catalyst.
2. The method for preparing a composite alumina catalyst according to claim 1, wherein the χ -Al 2 O 3 The particles have a size of less than or equal to 50 microns.
3. The method for preparing a composite alumina catalyst according to claim 1, wherein the χ -Al 2 O 3 Particle and cluster gamma-Al 2 O 3 The soaking time of the mixture in the alkaline solution is 2-24 hours.
4. The method for preparing a composite alumina catalyst according to claim 1, wherein a microwave drying method is adopted when the drying is performed, and the time of the microwave drying is 2-30 minutes.
5. The method for producing a composite alumina catalyst according to claim 1, wherein a temperature rise rate is 3 ℃/min to 15 ℃/min when the calcination is performed.
6. The method for producing a composite alumina catalyst according to claim 1, wherein, when the firing is performed, a firing final temperature is 450 ℃ to 500 ℃, and a holding time at the firing final temperature is 2 to 24 hours.
7. A composite alumina catalyst, characterized in that the composite alumina catalyst adopts the preparation method according to any one of claims 1 to 6The preparation method comprises the steps of: X-Al 2 O 3 And gamma-Al 2 O 3 。
8. Use of the composite alumina catalyst of claim 7 in a claus reaction process;
the application comprises: SO as to contain SO 2 、H 2 S and N 2 Introducing the mixture into a fixed bed reactor filled with the composite alumina catalyst to perform the claus reaction.
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