WO2018227362A1 - 一种钒基催化剂及其制备方法 - Google Patents

一种钒基催化剂及其制备方法 Download PDF

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Publication number
WO2018227362A1
WO2018227362A1 PCT/CN2017/088011 CN2017088011W WO2018227362A1 WO 2018227362 A1 WO2018227362 A1 WO 2018227362A1 CN 2017088011 W CN2017088011 W CN 2017088011W WO 2018227362 A1 WO2018227362 A1 WO 2018227362A1
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Prior art keywords
vanadium
based catalyst
diatomaceous earth
silica
ultra
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PCT/CN2017/088011
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English (en)
French (fr)
Inventor
田先国
魏士新
董天雷
殷惠琴
谢天明
贺健
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Application filed by China Petroleum and Chemical Corp, Research Institute of Nanjing Chemical Industry Group Co Ltd filed Critical China Petroleum and Chemical Corp
Priority to US16/622,448 priority Critical patent/US10940462B2/en
Priority to PCT/CN2017/088011 priority patent/WO2018227362A1/zh
Priority to DE112017007638.2T priority patent/DE112017007638T5/de
Priority to CN201780092053.2A priority patent/CN111065458B/zh
Publication of WO2018227362A1 publication Critical patent/WO2018227362A1/zh
Anticipated expiration legal-status Critical
Priority to DKPA201901553A priority patent/DK180890B1/en
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/78—Preparation by contact processes characterised by the catalyst used
    • C01B17/79—Preparation by contact processes characterised by the catalyst used containing vanadium
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to the technical field of catalyst preparation, in particular to a vanadium-based catalyst and a preparation method thereof.
  • the vanadium catalyst is used in the sulfuric acid production unit to oxidize SO 2 to SO 3 .
  • the traditional vanadium catalyst is a vanadium-potassium (sodium)-silicon system, with vanadium pentoxide as the active component, potassium sulfate and sodium sulfate as auxiliary agents, and diatomaceous earth as the carrier.
  • the vanadium catalyst is packed in a converter of a sulfuric acid production unit to convert SO 2 into SO 3 , and the operating temperature is generally required to be higher than 410 ° C and not more than 600 ° C, which is advantageous for exerting the activity of the catalyst and increasing the conversion rate of SO 2 .
  • the vanadium catalyst is produced by dissolving KOH with steam, and preparing a KVO 3 and KOH mixed solution (referred to as vanadium water) in accordance with V 2 O 5 under hot boiling conditions, and then neutralizing the vanadium water with sulfuric acid.
  • a colloidal precipitate of V 2 O 5 and K 2 SO 4 was obtained.
  • the colloidal precipitate and the auxiliary agent, the purified diatomaceous earth and the like are added into the grinding machine according to the prescribed ratio, uniformly mixed, compacted and compacted to become a plastic material, and then finished into a finished product by the steps of extrusion, drying, roasting, sieving and packaging.
  • the active component vanadium pentoxide is added in the form of solid or colloidal form of vanadium pentoxide or ammonium vanadate or ammonium polyvanadate, and is mixed with other components, and the solid mixture is difficult to obtain a group.
  • the homogeneous distribution of materials affects the catalytic efficiency of the active components.
  • all vanadium sulfate catalysts are based on diatomaceous earth.
  • the quality of natural diatomite is very unstable due to geological origin.
  • the pore size distribution of natural diatomite is wide (refer to Table 1).
  • the stability is not uniform, and thus when the catalyst is prepared as a carrier, the dispersibility of the active component is not satisfactory.
  • the treated purified diatomaceous earth can serve as a vanadium catalyst support, the stability of the performance of the catalyst is affected by natural instability.
  • an object of the present invention is to provide a vanadium-based catalyst and a preparation method thereof, which can produce a higher catalytic activity by improving the uniformity of distribution of active components and improving the stability of the carrier.
  • the thermal stability of the catalyst especially suitable for the SO 2 oxidation to SO 3 reaction, can meet the needs of the total conversion of SO 2 in the production of sulfuric acid, has a high application value in the production of sulfuric acid.
  • the invention provides a vanadium-based catalyst comprising: an active phase supported on a support, wherein the active phase comprises vanadium oxide, potassium sulfate, sodium sulfate, and an auxiliary agent, the carrier comprising ultra-large pore silica and
  • the diatomaceous earth has an average pore diameter of 100-500 nm, and the diatomaceous earth is a purified diatomaceous earth having a silica content of 85% or more after purification.
  • the ultra-large pore silica has an average pore diameter of from 150 to 400 nm.
  • diatomaceous earth in a particular area can be treated to obtain refined diatomaceous earth using physical and chemical methods well known in the art.
  • the refined diatomaceous earth is at least one of Zhejiang diatomaceous earth, Yunnan diatomaceous earth, and northeast diatomaceous earth obtained by physical and/or chemical treatment.
  • the inventors of the present application have found that by using a technical solution of super macroporous silica and diatomaceous earth, it is possible to form a carrier having excellent formability and stability, uniform pore size, and stable pore structure, thereby forming a catalyst.
  • a catalyst with excellent performance This is because, on the one hand, the ultra-large pore silica having a crystal structure can be corrected by the spatial structure of the amorphous diatomaceous earth to obtain a carrier having a narrow pore size distribution, thereby reducing the instability of the diatomaceous earth to the performance of the catalyst.
  • the effect is beneficial to improve the loading effect of the active phase on the carrier; on the other hand, the ultra-large pore silica can also serve as a binder to improve the formability, stability and strength of the diatomaceous earth.
  • the technical specifications of commonly used macroporous silica are shown in Table 2. It can be seen that the existing macroporous silica has a particle diameter of about 12 to 50 nm.
  • the ultraporous silica used in the present invention has an average pore diameter of from 100 to 500 nm, preferably from 150 to 400 nm.
  • the ultra-large pore silica in the pore size range is particularly suitable for supporting and dispersing an active phase composed of vanadium oxide, potassium sulfate, etc., and thus a vanadium-based catalyst excellent in catalytic performance can be obtained.
  • the active phase is contained in an amount of 30 to 40% by weight, and the carrier contains The amount is 60-70% by weight.
  • the content of the vanadium oxide is 6.5 wt% to 8.5 wt% based on the total weight of the vanadium-based catalyst; the molar ratio of potassium element to vanadium element is (2.5-4.0) ): 1; the auxiliary is contained in an amount of 0.5 to 2.0% by weight.
  • the sodium sulfate is present in an amount of from 3.0 to 6.0% by weight.
  • the inventors of the present application have found through research that the low temperature activity of the catalyst can be improved by containing a specific content of sodium sulfate. If the content of sodium sulfate is less than 3.0% by weight, the increase in low temperature activity is insufficient; if the content of sodium sulfate is higher than 6.0% by weight, the low temperature activity is close to the peak value, and the increase is not significant.
  • the content of the super macroporous silica is 8.0 to 20.0% by weight based on the total weight of the vanadium-based catalyst.
  • Another aspect of the invention provides a method for preparing the above vanadium-based catalyst, comprising:
  • step 2) mixing the neutralization reaction product of step 1) with a carrier and sodium sulfate, and rolling, extruding, drying and calcining to obtain a vanadium-based catalyst comprising super-large pore silica and refined diatomaceous earth. ;
  • the ultra-large pore silica has an average pore diameter of 100-500 nm, and the diatomaceous earth is refined diatomaceous earth having a silica content of 85% or more after purification;
  • an adjuvant compound is added in step 1) and/or step 2).
  • potassium sulfite is added when preparing the mixed solution.
  • the molar ratio of the potassium sulfite to the potassium vanadate is 1: (0.9-1) ).
  • the above neutralization reaction product is a colloidal precipitate containing V 2 O 5 and K 2 SO 4
  • the pentavalent vanadium is reduced.
  • the tetravalent vanadium ion is formed such that the above neutralization reaction product is a solution containing VOSO 4 and K 2 SO 4 .
  • the reaction product in the solution state is mixed with the carrier, and the mixing is more sufficient and the loading effect is better than the manner in which the colloidal precipitate is mixed with the carrier.
  • potassium sulfite as a reducing agent not only does not introduce other components, but also provides potassium as an active component, and avoids the use of gas SO 2 relative to other reducing agents such as gas SO 2 , oxalic acid, and the like.
  • the reduction of secondary pollution and the high cost of oxalic acid reduction have the advantages of environmental protection, low pollution and low cost.
  • the weight ratio of the ultra-large pore silica to the diatomaceous earth is (5-40): (60-95), preferably (12) -35): (65-88).
  • the inventors of the present application have found that by limiting the weight ratio of ultra-large pore silica to diatomaceous earth within the above specific range, it is advantageous to obtain a preferable correction effect of ultra-large pore silica on diatomaceous earth. If the proportion of the ultra-large pore silica is less than 5%, the effect of correcting the particle size structure and the particle size distribution of the diatomaceous earth cannot be surely achieved. Another On the other hand, if the proportion of the ultra-large pore silica is more than 40%, the formability and stability of the catalyst may be affected.
  • the preparation of the ultra-large pore silica comprises the step of using polystyrene colloidal microspheres having a particle diameter of from 120 nm to 550 nm in a silica sol.
  • the polystyrene colloidal microspheres having a particle diameter of from 120 nm to 550 nm which are used in the silica sol are decomposed in a subsequent calcination step, thereby forming ultra-large pore silica having a pore diameter of from 100 to 500 nm.
  • the auxiliary compound is at least one selected from the group consisting of a phosphorus-containing compound and a cerium-containing compound, preferably at least one selected from the group consisting of phosphoric acid, cerium hydroxide, and barium sulfate.
  • the inventors of the present application have found through research that the low-temperature activity of the catalyst can be further improved by using a specific content of the phosphorus-containing compound and/or the ruthenium-containing compound as an auxiliary compound.
  • the adjuvant compound is basic, preferably added in step 1); the adjuvant compound is acidic, optionally added in step 1) or step 2).
  • the present invention provides a method for producing SO 3 by SO 2 oxidation, comprising: contacting a gas stream comprising SO 2 with the vanadium-based catalyst to obtain a gas product comprising SO 3 .
  • the above vanadium-based catalyst can be applied to a converter of a sulfuric acid production unit for conversion of SO 2 to SO 3 .
  • experimental materials used include:
  • Yunnan diatomaceous earth YX04 produced by Yunnan Diatomite Products Factory;
  • diatomaceous earth In order to meet the requirements of diatomaceous earth as a carrier, natural diatomaceous earth must be processed to reduce the content of clay minerals and detrital minerals and increase the proportion of diatom shells.
  • the raw diatomaceous earth is generally separated by beating, swirling, and then treated with sulfuric acid to obtain purified diatomaceous earth.
  • the average pore diameter is an average pore diameter measured and calculated according to a mercury intrusion method (GBT 21650.1 mercury intrusion method and gas adsorption method for measuring pore size distribution and porosity of a solid material, Part 1 : mercury intrusion method).
  • TMOS methyl orthosilicate
  • methanol methyl orthosilicate
  • a certain concentration of hydrochloric acid was added to the reaction flask, N 2 was introduced , and the temperature was raised to reflux temperature for 2 h. Finally, it was naturally cooled to room temperature to obtain a colorless transparent SiO 2 sol.
  • the polystyrene colloidal microspheres having a particle diameter of 260 nm to 280 nm were immersed in the SiO 2 sol for 10 min, and after suction filtration, the filtered solid was dried at 70 ° C for 60 min.
  • the above soaking, suction filtration and drying processes were repeated 3 times.
  • the dried product after treatment is placed in a tube furnace, and heated to a temperature of 3 ° C / min to 300 ° C under a condition of passing air, at a constant temperature for 4 h, and then heated to 600 ° C, at a constant temperature of 3 h, and then naturally cooled.
  • Ultra-large pore silica having an average pore diameter of 240 nm.
  • Ultra-large pore silica was prepared in the same manner as in Preparation Example 1, except that the particle diameter of the polystyrene colloidal microspheres was from 170 nm to 180 nm, and the obtained ultra-large pore silica had an average pore diameter of 150 nm.
  • Control under the conditions of air, slowly increase temperature ( ⁇ 5 °C / min) to 300 ° C, constant temperature 5h, and then heat to 570 ° C, constant temperature 5h, after cooling to obtain ultra-large pore silica, the pore diameter is 300nm.
  • Ultra-large pore silica was prepared in the same manner as in Preparation Example 3 except that the particle diameter of the polystyrene colloidal microspheres was from 420 nm to 445 nm, and the obtained ultra-large pore silica had an average pore diameter of 400 nm.
  • the KOH was melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) was prepared under hot boiling conditions with V 2 O 5 .
  • the vanadium water obtained had a V 2 O 5 concentration of 266 g/L and a K 2 O/V 2 O 5 molar ratio of 3.7.
  • 30.1 ml of vanadium water was neutralized with 17.9 ml of sulfuric acid (sulphuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 to form a colloidal precipitate.
  • V 2 O 5 is 8.0 wt%
  • K 2 O/V 2 O 5 is 3.7 (molar ratio)
  • Na 2 SO 4 is 3.7 wt%
  • P 2 O 5 is 1%
  • super large pores are The silica was 8.0 wt%, and the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained is 266 g/L, K 2 .
  • the molar ratio of O/V 2 O 5 was 4.0.
  • 28.2 ml of vanadium water was neutralized with 18.2 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 to form a colloidal precipitate.
  • V 2 O 5 was 7.5%
  • K 2 O/V 2 O 5 was 4.0 (molar ratio)
  • Na 2 SO 4 was 4.1%
  • barium sulfate was 0.9%
  • ultra-large pore silica was 13.0. %
  • the balance is refined Yunnan diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained is 266 g/L, K 2 .
  • the molar ratio of O/V 2 O 5 was 3.5.
  • vanadium water was neutralized with 17.4 ml of sulfuric acid (sulphuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 , and the colloidal precipitate was 5.5g Na 2 SO 4 , 1ml phosphoric acid, 18.0g of super-large pore silica prepared in Preparation Example 3, 47.0g of refined Zhejiang diatomaceous earth were added to the mill and mixed uniformly, and the water was compacted to become a plastic material, and then extruded, The drying and calcining steps were carried out to prepare 100 g of a vanadium catalyst.
  • sulfuric acid sulphuric acid solution mixed with sulfuric acid and water in a volume of 1:1
  • V 2 O 5 is 8.2% by weight
  • K 2 O/V 2 O 5 is 3.5 (molar ratio)
  • Na 2 SO 4 is 5.5 wt%
  • P 2 O 5 is 1 wt%
  • the ultra large pores are The silica was 18.0%, and the balance was refined Zhejiang diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained is 266 g/L, K 2 .
  • the molar ratio of O/V 2 O 5 was 3.8.
  • 29.3 ml of vanadium water and 1.5 g of cesium hydroxide were uniformly mixed, and neutralized with 19.1 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to obtain V 2 O 5 and K 2 SO 4 .
  • the colloidal precipitate was mixed with 3.1 g of Na2SO4, 10.6 g of super macroporous silica prepared in Preparation Example 4, and 55.5 g of refined northeast diatomaceous earth into a roller, uniformly mixed with water, and compacted to become a plastic material.
  • the stripping, drying, and baking steps were carried out to prepare 100 g of a vanadium-based catalyst.
  • V 2 O 5 is 7.8 wt%
  • K 2 O/V 2 O 5 is 3.8 (molar ratio)
  • Na 2 SO 4 is 3.1 wt%
  • barium sulfate is 1.8 wt%
  • super macroporous oxidation The silicon content was 10.6 wt%, and the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , 71.2 g of potassium sulfite is added, and V 2 O 5 of vanadium water is obtained after dissolution.
  • the concentration was 266 g/L, and the molar ratio of K 2 O/V 2 O 5 was 3.5.
  • 30.8 ml of vanadium water was neutralized with 22.4 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 5.5 g of Na.
  • V 2 O 5 is 8.2% by weight
  • K 2 O/V 2 O 5 is 3.5 (molar ratio)
  • Na 2 SO 4 is 5.5 wt%
  • P 2 O 5 is 1 wt%
  • the ultra large pores are The silica was 18.0% by weight, and the balance was refined Zhejiang diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and 67.7 g of potassium sulfite is added, and V 2 O 5 of vanadium water obtained by dissolving is added.
  • the concentration was 266 g/L, and the molar ratio of K 2 O/V 2 O 5 was 3.2.
  • 29.3 ml of vanadium water was neutralized with 19.9 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 6.0 g of Na.
  • V 2 O 5 is 7.8 wt%
  • K 2 O/V 2 O 5 is 3.2 (molar ratio)
  • Na 2 SO 4 is 6.0 wt%
  • P 2 O 5 is 1 wt%
  • super large pores are The silica was 11.2% by weight, and the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and 69.5 g of potassium sulfite is added to dissolve the V 2 O 5 of the vanadium water.
  • the concentration was 266 g/L, and the molar ratio of K 2 O/V 2 O 5 was 3.7.
  • 30.1 ml of vanadium water was neutralized with 22.8 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 3.7 g of Na.
  • V 2 O 5 is 8.0 wt%
  • K 2 O/V 2 O 5 is 3.7 (molar ratio)
  • Na 2 SO 4 is 3.7 wt%
  • barium sulfate is 1.6%
  • ultra-macroporous silica It is 8.0 wt%, and the balance is refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the prepared vanadium water is 266 g/L, K 2 O.
  • the molar ratio of /V 2 O 5 was 2.7.
  • 30.1 ml of vanadium water was neutralized with 13.1 ml of 1:1 (vol) sulfuric acid to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 , and the colloidal precipitate was mixed with 82.0 g of refined northeast diatomaceous earth into the mill. Uniform, adding water and compacting to become a plastic material, and then 100 g of vanadium catalyst by extrusion, drying and roasting.
  • V 2 O 5 was 8.0 wt%
  • K 2 O/V 2 O 5 was 2.7 (molar ratio)
  • the balance was refined northeast diatomaceous earth.
  • vanadium water a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , 69.5 g of potassium sulfite is added, and V 2 O 5 of vanadium water is obtained after dissolution.
  • the concentration was 266 g/L, and K 2 O/V 2 O 5 was 2.7.
  • 30.1 ml of vanadium water was neutralized with 18.0 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was refined with 82.0 g.
  • the diatomite in the northeast is mixed into the mill and uniformly mixed with water to form a plastic material.
  • 100 g of vanadium catalyst is prepared by extrusion, drying and calcination.
  • V 2 O 5 was 8.0 wt%
  • K 2 O/V 2 O 5 was 2.7 (molar ratio)
  • the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and 65.2 g of potassium sulfite is added, and the V 2 O 5 concentration of the vanadium water obtained after dissolution is obtained. It was 266 g/L, and K 2 O/V 2 O 5 was 3.5. Then, 28.2 ml of vanadium water was neutralized with 20.5 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 3.5 g of Na.
  • vanadium water a mixed solution of KVO 3 and KOH
  • V 2 O 5 is 7.5 wt%
  • K 2 O/V 2 O 5 is 3.5 (molar ratio)
  • Na 2 SO 4 is 3.5 wt%
  • P 2 O 5 is 1 wt%
  • the balance is Refined Yunnan diatomaceous earth.
  • vanadium water a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained after dissolution is 266 g/L, K 2 . O/V 2 O 5 is 2.7.
  • 30.1 ml of vanadium water was neutralized with 13.1 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 1.5 g of Na. 2 SO 4 and 80.3g refined Zhejiang diatomaceous earth was added into the mill and mixed uniformly.
  • the water was compacted and compacted to become a plastic material.
  • 100 g of vanadium catalyst was prepared by extrusion, drying and calcination.
  • V 2 O 5 was 8.0 wt%
  • K 2 O/V 2 O 5 was 2.7 (molar ratio)
  • Na 2 SO 4 was 1.5 wt%
  • the balance was refined Zhejiang diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and 67.7 g of potassium sulfite is added, and V 2 O 5 of vanadium water obtained by dissolving is added.
  • the concentration was 266 g/L, and the molar ratio of K 2 O/V 2 O 5 was 3.2.
  • 29.3 ml of vanadium water was neutralized with 19.9 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 6.0 g of Na.
  • V 2 O 5 is 7.8 wt%
  • K 2 O/V 2 O 5 is 3.2 (molar ratio)
  • Na 2 SO 4 is 6.0 wt%
  • P 2 O 5 is 1 wt%
  • super large pores are The silica was 5.0 wt%, and the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and 67.7 g of potassium sulfite is added, and V 2 O 5 of vanadium water obtained by dissolving is added.
  • the concentration was 266 g/L, and the molar ratio of K 2 O/V 2 O 5 was 3.2.
  • 29.3 ml of vanadium water was neutralized with 19.9 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a mixture of VOSO 4 and K 2 SO 4 , and the mixture was mixed with 6.0 g of Na.
  • V 2 O 5 is 7.8 wt%
  • K 2 O/V 2 O 5 is 3.2 (molar ratio)
  • Na 2 SO 4 is 6.0 wt%
  • P 2 O 5 is 1 wt%
  • macroporous The silica was 11.2% by weight, and the balance was refined northeast diatomaceous earth.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained after dissolution is 266 g/L, K.
  • the molar ratio of 2 O/V 2 O 5 was 3.2.
  • 30.1 ml of vanadium water was neutralized with 15.5 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 , and the colloidal precipitate was precipitated.
  • V 2 O 5 was 8.0 wt%
  • K 2 O/V 2 O 5 was 3.2 (molar ratio)
  • P 2 O 5 was 1 wt%
  • the balance was ultra-large pore silica.
  • the KOH is melted with steam, and a mixed solution of KVO 3 and KOH (referred to as vanadium water) is prepared under hot boiling conditions with V 2 O 5 , and the V 2 O 5 concentration of the vanadium water obtained after dissolution is 266 g/L, K.
  • the molar ratio of 2 O/V 2 O 5 was 3.2.
  • 28.2 ml of vanadium water was neutralized with 14.6 ml of sulfuric acid (sulfuric acid solution mixed with sulfuric acid and water in a volume of 1:1) to prepare a colloidal precipitate of V 2 O 5 and K 2 SO 4 , and the colloidal precipitate was precipitated.
  • V 2 O 5 is 7.5 wt%
  • K 2 O/V 2 O 5 is 3.2 (molar ratio)
  • Na 2 SO 4 is 6.0 wt%
  • P 2 O 5 is 1 wt%
  • the silica was 30.0% by weight, and the balance was refined Yunnan diatomaceous earth.
  • the catalysts of the above examples and comparative examples were prepared into catalyst samples having a particle size of ⁇ 5 ⁇ 5 to 8 mm, and the activity test was carried out under the following conditions, and the activity was expressed by the conversion ratio of SO 2 .
  • the test results are shown in Table 1.
  • Converter adopts a jacketed single-tube reactor with a diameter of ⁇ 36 ⁇ 2mm, and the thermocouple is located at the center of the converter, and its diameter is ⁇ 8 ⁇ 1.5mm;
  • volume percentage of intake SO 2 10%, the balance is air;
  • Activity detection temperature 440 ° C.
  • the strength was measured in accordance with the measurement of the crush resistance of the HG/T 2782 fertilizer catalyst particles.
  • the vanadium catalyst prepared by the method of the invention has significantly higher activity than the conventional vanadium-based catalyst, and is applied to a converter of a sulfuric acid production unit, which can improve the conversion rate of SO 2 and satisfy the total production of SO 2 by sulfuric acid production. The need for conversion rates.

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Abstract

一种钒基催化剂，包括：负载在载体上的活性相，活性相包括氧化钒、硫酸钾、硫酸钠以及助剂，载体包括超大孔二氧化硅和硅藻土，超大孔二氧化硅的平均孔径为 100-500nm，硅藻土为经精制后二氧化硅含量达到85%以上的精制硅藻土。该钒基催化剂的制备方法，包括：1）将钒酸钾和氢氧化钾混合，制成的混合溶液与硫酸发生中和反应；2）将步骤 1）的中和反应产物与载体和硫酸钠混合，经碾压、挤条、干燥和焙烧后，制得钒基催化剂；其中，在步骤 l）和/或步骤 2）中加入助剂化合物。

Description

一种钒基催化剂及其制备方法 技术领域
本发明涉及催化剂制备的技术领域，尤其涉及一种钒基催化剂及其制备方法。
背景技术
钒催化剂用于硫酸生产装置中将SO2氧化转化为SO3。传统钒催化剂为钒—钾(钠)—硅体系，以五氧化二钒为活性组分，硫酸钾、硫酸钠为助剂，硅藻土为载体。钒催化剂装填在硫酸生产装置的转化器中，将SO2转化为SO3，操作温度一般要求高于410℃，不超过600℃，有利于发挥催化剂的活性，提高SO2的转化率。
目前钒催化剂的制造方法为将KOH用蒸汽溶化，并与V2O5在热煮条件下制得符合要求的KVO3与KOH混合溶液(简称钒水)，然后将钒水用硫酸中和制得V2O5和K2SO4胶体沉淀物。然后按规定比例将胶体沉淀物与助剂、精制硅藻土等加入碾子中混合均匀，碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧、过筛和包装等工序制成成品。在上述方法中，活性组分五氧化二钒都是以五氧化二钒或钒酸铵、多钒酸铵的固体或胶体形态加入，与其他组分进行混碾，固固混合很难得到组分分布均匀的物料，影响了活性组分的催化效率。此外，所有的硫酸钒催化剂都是以硅藻土为载体，天然硅藻土质量由于地质成因存在很大的不稳定性，天然硅藻土的孔径分布较宽(参照表1)，孔径结构不稳定也不均匀，因而将其作为载体制备催化剂时，活性组分的分散性不理想。虽然经过处理后的精制硅藻土能够作为钒催化剂载体，但由于天然的不稳定性影响了催化剂的性能的稳定性。
表1天然硅藻土的孔径分布
孔径范围 8-50nm 50-100nm 100-300nm 300-600nm 600-900nm ＞900nm
比例 10-15％ 20-25％ 25-30％ 20-25％ 10-15％ 5-10％
发明内容
鉴于上述现有技术中存在的问题，本发明的目的在于提供一种钒基催化剂及其制备方法，通过改善活性组分分布的均匀性和提高载体的稳定性，能够制备出具有更高催化活性和热稳定性的催化剂，特别适用于SO2氧化制SO3的反应，可以满足硫酸生产中对SO2总转化率的需要，在硫酸生产中具有很高的应用价值。
本发明一方面提供一种钒基催化剂，包括：负载在载体上的活性相，其中，所述活性相包括氧化钒、硫酸钾、硫酸钠以及助剂，所述载体包括超大孔二氧化硅和硅藻土，所述超大孔二氧化硅的平均孔径为100-500nm，所述硅藻土为经精制后二氧化硅含量达到85％以上的精制硅藻土。
在本发明的一个优选的实施方式中，所述超大孔二氧化硅的平均孔径为150-400nm。
根据本发明，可采用本领域公知的物理、化学方法对特定地区的硅藻土进行处理以获得精制硅藻土。优选地，所述精制硅藻土是经过物理和/或化学方法处理得到的浙江硅藻土、云南硅藻土、东北硅藻土中的至少一种。
本申请的发明人经研究发现，通过使用超大孔二氧化硅和硅藻土复配的技术方案，能够形成具有优异的成形性和稳定性，孔径大小均匀，孔径结构稳定的载体，进而形成催化性能优异的催化剂。这是由于，一方面具有晶体结构的超大孔二氧化硅能够无定型的硅藻土的空间结构进行校正，得到孔径分布较窄的载体，从而减少了硅藻土的不稳定性对催化剂性能的影响，有利于改善活性相在载体上的负载效果；另一方面，超大孔二氧化硅还能够作为粘结剂改善硅藻土的成形性能、稳定性能和强度。
目前，常用的大孔二氧化硅的技术指标如表2所示。可以看出，现有的大孔二氧化硅的粒径在12-50nm左右。而本发明所使用的超大孔二氧化硅的平均孔径为100-500nm，优选为150-400nm。在该孔径范围内的超大孔二氧化硅，特别适合于负载和分散氧化钒、硫酸钾等组成的活性相，因而能够获得催化性能优异的钒基催化剂。
表2大孔二氧化硅技术指标
Figure PCTCN2017088011-appb-000001
备注：1nm＝10A
在本发明的一个优选的实施方式中，所述活性相的含量为30-40wt％，所述载体的含 量为60-70wt％。
在本发明的另一个优选的实施方式中，基于所述钒基催化剂的总重量，所述氧化钒的含量为6.5wt％-8.5wt％；钾元素与钒元素的摩尔比为(2.5-4.0):1；所述助剂的含量为0.5-2.0wt％。
在本发明的另一个优选的实施方式中，所述硫酸钠的含量为3.0-6.0wt％。
本申请的发明人经研究发现，通过含有特定含量的硫酸钠，能够提高催化剂的低温活性。若硫酸钠的含量不足3.0wt％，则低温活性增加不够；若硫酸钠的含量高于6.0wt％，则低温活性接近峰值，提高不明显。
在本发明的另一个优选的实施方式中，基于所述钒基催化剂的总重量，所述超大孔二氧化硅的含量为8.0-20.0wt％。
本发明另一方面提供上述钒基催化剂的制备方法，包括：
1)将钒酸钾和氢氧化钾混合，制成的混合溶液与硫酸发生中和反应；
2)将步骤1)的中和反应产物与载体和硫酸钠混合，经碾压、挤条、干燥和焙烧后，制得钒基催化剂，所述载体包括超大孔二氧化硅和精制硅藻土；
其中，所述超大孔二氧化硅的平均孔径为100-500nm，所述硅藻土为经精制后二氧化硅含量达到85％以上的精制硅藻土；
其中，在步骤1)和/或步骤2)中加入助剂化合物。
在本发明的一个优选的实施方式中，在步骤1)中，制备混合溶液时加入亚硫酸钾，优选的，所述亚硫酸钾与所述钒酸钾的摩尔比为1:(0.9-1)。
根据本发明，在未加入亚硫酸钾的情况下，上述中和反应产物为含有V2O5和K2SO4的胶体沉淀物，在加入亚硫酸钾的情况下，五价的钒被还原成四价的钒离子，因而使上述中和反应产物为含有VOSO4和K2SO4的溶液。以溶液态的反应产物与载体混合，相比于胶体沉淀物与载体混合的方式，混合更为充分，负载效果更好。另外，作为还原剂的亚硫酸钾，不仅没有引入其他的组分，还能够提供作为活性组分的钾元素，相对于采用其他还原剂，如气体SO2、草酸等，避免了使用气体SO2还原产生二次污染以及草酸还原的高成本，具有环保、低污染、低成本的优势。
在本发明的一个优选的实施方式中，在所述载体中，所述超大孔二氧化硅和所述硅藻土的重量比为(5-40)：(60-95)，优选为(12-35)：(65-88)。
本申请的发明人经研究发现，通过将超大孔二氧化硅和硅藻土的重量比限定在上述特定范围内，有利于获得超大孔二氧化硅对硅藻土的较为理想的校正效果。若超大孔二氧化硅的比例小于5％，则不能确实地起到对硅藻土的粒径结构和粒径分布的校正作用。另一 方面，若超大孔二氧化硅的比例大于40％，则恐会影响催化剂的成形性和稳定性。
在本发明的另一个优选的实施方式中，所述超大孔二氧化硅的制备包括在二氧化硅溶胶中使用粒径在120nm-550nm的聚苯乙烯胶体微球的工序。根据本发明，在二氧化硅溶胶中使用的粒径在120nm-550nm的聚苯乙烯胶体微球在后续的焙烧工序中分解，由此形成孔径在100-500nm的超大孔二氧化硅。
在本发明的另一个优选的实施方式中，所述助剂化合物选自含磷化合物和含铯化合物中的至少一种，优选自磷酸、氢氧化铯和硫酸铯中的至少一种。
本申请的发明人经研究发现，通过使用特定含量的含磷化合物和/或含铯化合物作为助剂化合物，能够进一步提高催化剂的低温活性。
根据本发明，所述助剂化合物呈碱性，优选在步骤1)中加入；所述助剂化合物呈酸性，可任选地在步骤1)或步骤2)中加入。
本发明再一方面提供一种SO2氧化制SO3的方法，包括：将包含SO2的气流与上述钒基催化剂接触，得到包含SO3的气体产物。
根据本发明，可将上述钒基催化剂应用于硫酸生产装置的转化器中，用于SO2到SO3的转化。
本发明的其它特征和优点将在随后的说明书中阐述，并且部分地从说明书中变得显而易见，或者通过实施本发明而了解。本发明的目的和其他优点可通过在说明书、权利要求书以及附图中所特别指出的结构来实现和获得。
具体实施方式
以下将结合实施例来详细说明本发明的实施方式，借此对本发明如何应用技术手段来解决技术问题，并达成技术效果的实现过程能充分理解并据以实施。需要说明的是，只要不构成冲突，本发明中的各个实施例以及各实施例中的各个特征可以相互结合，所形成的技术方案均在本发明的保护范围之内。
在以下实施方式中，所使用的实验原料包括：
东北硅藻土：吉林省长白硅藻土有限责任公司生产的CB05；
云南硅藻土：云南硅藻土制品厂生产的YX04；
浙江硅藻土：嵊州市华力硅藻土制品有限公司生产的CD02。
为了达到硅藻土作为载体的要求，必须对天然硅藻土进行必要的加工处理，减少粘土矿物和碎屑矿物的含量，提高硅藻壳体的比例。一般将原料硅藻土经打浆、旋流分离，再经硫酸处理，制得精制硅藻土。
其他未列出的实验材料均为市售产品。
根据本发明，所述平均孔径为按照压汞法(GBT 21650.1压汞法和气体吸附法测定固体材料孔径分布和孔隙度第1部分：压汞法的规定)进行测定与计算得到的平均孔径。
预备例1
在装有搅拌器及回流冷凝管的250mL三口瓶中，加入75g正硅酸甲酯(TMOS)和65g甲醇，搅拌均匀。把一定浓度的盐酸加入到反应瓶中，通入N2，升温至回流温度反应2h。最后自然冷却至室温，得到无色透明的SiO2溶胶。
将粒径为260nm-280nm的聚苯乙烯胶体微球浸泡在SiO2溶胶中10min，抽滤后，将抽滤后的固体在70℃下干燥60min。上述浸泡、抽滤及干燥过程重复3次。将处理后的干燥产物置于管式炉中，在通空气的条件下，以3℃/min的速度升温至300℃，恒温4h，再升温至600℃，恒温3h，自然冷却后即制得超大孔二氧化硅，平均孔径为240nm。
预备例2
按照与预备例1相同的方式制备超大孔二氧化硅，不同之处在于聚苯乙烯胶体微球的粒径为170nm-180nm，制得的超大孔二氧化硅的平均孔径为150nm。
预备例3
以正硅酸乙酯为硅源，按n(Si(OEt)4)：n(EtOH)：n(HCl)：n(H2O)＝l：3.9：0.3：1.8的比例制成透明SiO2溶胶.将SiO2溶胶滴加到粒径为320nm-340nm的聚苯乙烯胶体微球中，抽滤后，将抽滤后的固体在60～70℃干燥60min，重复多次，采用程序升温控制，在通空气的条件下，缓慢升温(<5℃/min)至300℃，恒温5h，再升温至570℃，恒温5h，冷却后即制得超大孔二氧化硅，孔径为300nm。
预备例4
按照与预备例3相同的方式制备超大孔二氧化硅，不同之处在于聚苯乙烯胶体微球的粒径为420nm-445nm，制得的超大孔二氧化硅的平均孔径为400nm。
实施例1
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)。制得的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.7。然后将30.1ml的 钒水用17.9ml硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)的中和制得V2O5和K2SO4的胶体沉淀物，将胶体沉淀物与3.7g Na2SO4、1ml磷酸、8.0g预备例1制备的超大孔二氧化硅和59.8g经过提纯的精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为3.7(摩尔比)，Na2SO4为3.7wt％，P2O5为1％，超大孔二氧化硅为8.0wt％，余量为精制东北硅藻土。
实施例2
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，制得的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为4.0。然后将28.2ml的钒水用18.2ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得V2O5和K2SO4的胶体沉淀物，将胶体沉淀物与4.1g Na2SO4、0.9g硫酸铯、13.0g预备例2制备的超大孔二氧化硅、52.7g精制云南硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为7.5％，K2O/V2O5为4.0(摩尔比)，Na2SO4为4.1％，硫酸铯为0.9％，超大孔二氧化硅为13.0％，余量为精制云南硅藻土。
实施例3
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，制得的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.5。然后将30.8ml的钒水用17.4ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得V2O5和K2SO4胶体沉淀物，将胶体沉淀物与5.5g Na2SO4、1ml磷酸、18.0g预备例3制备的超大孔二氧化硅、47.0g精制浙江硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为8.2wt％，K2O/V2O5为3.5(摩尔比)，Na2SO4为5.5wt％，P2O5为1wt％，超大孔二氧化硅为18.0％、余量为精制浙江硅藻土。
实施例4
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，制得的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.8。然后将29.3ml的钒水和1.5g氢氧化铯混合均匀，用19.1ml的硫酸(采用硫酸与水按照1∶1的体积混合 的硫酸溶液)中和制得V2O5和K2SO4胶体沉淀物，将胶体沉淀物与3.1g Na2SO4、10.6g预备例4制备的超大孔二氧化硅、55.5g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为7.8wt％，K2O/V2O5为3.8(摩尔比)，Na2SO4为3.1wt％，硫酸铯为1.8wt％，超大孔二氧化硅为10.6wt％、余量为精制东北硅藻土。
实施例5
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，加入71.2g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.5。然后将30.8ml的钒水用22.4ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与5.5g Na2SO4、1ml磷酸、18.0g预备例1制备的超大孔二氧化硅、47.0g精制浙江硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为8.2wt％，K2O/V2O5为3.5(摩尔比)，Na2SO4为5.5wt％，P2O5为1wt％，超大孔二氧化硅为18.0wt％、余量为精制浙江硅藻土。
实施例6
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，加入67.7g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.2。然后将29.3ml的钒水用19.9ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与6.0g Na2SO4、1ml磷酸、11.2g预备例2制备的超大孔二氧化硅、58.8g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为7.8wt％，K2O/V2O5为3.2(摩尔比)，Na2SO4为6.0wt％，P2O5为1wt％，超大孔二氧化硅为11.2wt％，余量为精制东北硅藻土。
实施例7
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，加入69.5g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.7。然后将30.1ml的钒水用22.8ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与3.7g Na2SO4、1.6g硫酸 铯、8.0g预备例1制备的超大孔二氧化硅、57.9g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为3.7(摩尔比)，Na2SO4为3.7wt％，硫酸铯为1.6％，超大孔二氧化硅为8.0wt％，余量为精制东北硅藻土。
对比例1
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，制备的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为2.7。然后将30.1ml的钒水用13.1ml1∶1(vol)的硫酸中和制得V2O5和K2SO4胶体沉淀物，将胶体沉淀物与82.0g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为2.7(摩尔比)，余量为精制东北硅藻土。
对比例2
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH混合溶液(简称钒水)，加入的69.5g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5为2.7。然后将30.1ml的钒水用18.0ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与82.0g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为2.7(摩尔比)，余量为精制东北硅藻土。
对比例3
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH混合溶液(简称钒水)，加入65.1g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5为3.5。然后将28.2ml的钒水用20.5ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与3.5g Na2SO4、1ml磷酸、73.5g精制云南硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为7.5wt％，K2O/V2O5为3.5(摩尔比)，Na2SO4为3.5wt％， P2O5为1wt％，余量为精制云南硅藻土。
对比例4
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH混合溶液(简称钒水)，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5为2.7。然后将30.1ml的钒水用13.1ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与1.5g Na2SO4、80.3g精制浙江硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为2.7(摩尔比)，Na2SO4为1.5wt％、余量为精制浙江硅藻土。
对比例5
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，加入67.7g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.2。然后将29.3ml的钒水用19.9ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与6.0g Na2SO4、1ml磷酸、5.0g预备例1制备的超大孔二氧化硅、65.9g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为7.8wt％，K2O/V2O5为3.2(摩尔比)，Na2SO4为6.0wt％，P2O5为1wt％，超大孔二氧化硅为5.0wt％，余量为精制东北硅藻土。
对比例6
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，加入67.7g亚硫酸钾，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.2。然后将29.3ml的钒水用19.9ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得VOSO4和K2SO4混合液，将该混合液与6.0g Na2SO4、1ml磷酸、11.2g大孔二氧化硅(型号：Ⅳ型、孔径：40-50nm)、58.8g精制东北硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为7.8wt％，K2O/V2O5为3.2(摩尔比)，Na2SO4为6.0wt％，P2O5为1wt％，大孔二氧化硅为11.2wt％，余量为精制东北硅藻土。
对比例7
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.2。然后将30.1ml的钒水用15.5ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得V2O5和K2SO4胶体沉淀物，将该胶体沉淀物与1ml磷酸、67.5g预备例1制备的超大孔二氧化硅加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为8.0wt％，K2O/V2O5为3.2(摩尔比)，P2O5为1wt％，余量为超大孔二氧化硅。
对比例8
将KOH用蒸汽溶化，并与V2O5在热煮条件下制得KVO3与KOH的混合溶液(简称钒水)，溶解后得到的钒水的V2O5浓度为266g/L，K2O/V2O5的摩尔比为3.2。然后将28.2ml的钒水用14.6ml的硫酸(采用硫酸与水按照1∶1的体积混合的硫酸溶液)中和制得V2O5和K2SO4胶体沉淀物，将该胶体沉淀物与6.0g Na2SO4、1ml磷酸、30.0g预备例1制备的超大孔二氧化硅、38.6g精制云南硅藻土加入碾子中混合均匀，加水碾压紧密，成为可塑性物料，再经挤条、干燥、焙烧工序制成100g钒基催化剂。
该钒基催化剂中，V2O5为7.5wt％，K2O/V2O5为3.2(摩尔比)，Na2SO4为6.0wt％，P2O5为1wt％，超大孔二氧化硅为30.0wt％，余量为精制云南硅藻土。
试验例1
将上述实施例和对比例的催化剂制成粒度为φ5×5～8mm的催化剂样品，并采用下述条件进行活性测试，以SO2的转化率表示活性的高低，测试结果如表1所示。
SO2转化率E，数值以％表示，按下面公式计算：
Figure PCTCN2017088011-appb-000002
式中：
Figure PCTCN2017088011-appb-000003
——反应器进口气体中二氧化硫体积分数的数值，以％表示；
Figure PCTCN2017088011-appb-000004
——反应器出口气体中二氧化硫体积分数的数值，以％表示。
转化器：采用夹套式单管反应器，其管径为φ36×2mm，测温热电偶套管位于转化器的中心，其管径为φ8×1.5mm；
催化剂装量：30ml；
空间速度：3600h；
进气SO2的体积百分数：10％、余量为空气；
系统压力：常压；
活性检测温度：440℃。
试验例2
强度按HG/T 2782化肥催化剂颗粒抗压碎力的测定的规定进行测定。
表2活性测试结果
样品 活性(SO2转化率)％ 强度(N/cm)
实施例1 67.8 75
实施例2 64.2 70
实施例3 63.6 68
实施例4 64.5 66
实施例5 65.0 69
实施例6 65.5 71
实施例7 67.5 72
对比例1 55.0 52
对比例2 58.8 57
对比例3 60.4 60
对比例4 56.4 54
对比例5 60.6 64
对比例6 59.8 61
对比例7 51.2 35
对比例8 56.1 48
由表1可知，采用本发明方法制备的钒催化剂的活性明显高于传统的钒基催化剂，将其应用于硫酸生产装置的转化器中，能提高SO2转化率，满足硫酸生产对SO2总转化率的需要。
虽然本发明所公开的实施方式如上，但所述的内容只是为了便于理解本发明而采用的实施方式，并非用以限定本发明。任何本发明所属技术领域内的技术人员，在不脱离本发明所公开的精神和范围的前提下，可以在实施的形式上及细节上作任何的修改与变化，但本发明的保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (11)

  1. 一种钒基催化剂，包括：负载在载体上的活性相，其中，所述活性相包括氧化钒、硫酸钾、硫酸钠以及助剂，所述载体包括超大孔二氧化硅和硅藻土，所述超大孔二氧化硅的平均孔径为100-500nm，所述硅藻土为经精制后二氧化硅含量达到85％以上的精制硅藻土。
  2. 根据权利要求1所述的钒基催化剂，其特征在于，所述超大孔二氧化硅的平均孔径为150-400nm。
  3. 根据权利要求1或2所述的钒基催化剂，其特征在于，所述活性相的含量为30-40wt％，所述载体的含量为60-70wt％。
  4. 根据权利要求1-3中任意一项所述的钒基催化剂，其特征在于，基于所述钒基催化剂的总重量，所述氧化钒的含量为6.5wt％-8.5wt％；钾元素与钒元素的摩尔比为(2.5-4.0):1；所述助剂的含量为0.5-2.0wt％；所述硫酸钠的含量为3.0-6.0wt％。
  5. 根据权利要求1-4中任意一项所述的钒基催化剂，其特征在于，基于所述钒基催化剂的总重量，所述超大孔二氧化硅的含量为8.0-20.0wt％。
  6. 一种根据权利要求1-5中任意一项所述钒基催化剂的制备方法，包括：
    1)将钒酸钾和氢氧化钾混合，制成的混合溶液与硫酸发生中和反应；
    2)将步骤1)的中和反应产物与载体和硫酸钠混合，经碾压、挤条、干燥和焙烧后，制得钒基催化剂，所述载体包括超大孔二氧化硅和硅藻土；
    其中，所述超大孔二氧化硅的平均孔径为100-500nm，所述硅藻土为经精制后二氧化硅含量达到85％以上的精制硅藻土；
    其中，在步骤1)和/或步骤2)中加入助剂化合物。
  7. 根据权利要求6所述的制备方法，其特征在于，在步骤1)中，制备混合溶液时加入亚硫酸钾，优选的，所述亚硫酸钾与所述钒酸钾的摩尔比为1:(0.9-1)。
  8. 根据权利要求6或7所述的制备方法，其特征在于，在所述载体中，所述超大孔二氧化硅和所述硅藻土的重量比为(6-20)：(40-55)，优选为(8-18)：(40-52)。
  9. 根据权利要求6-8中任意一项所述的制备方法，其特征在于，所述超大孔二氧化硅的制备包括在二氧化硅溶胶中使用粒径在120nm-550nm的聚苯乙烯胶体微球的工序。
  10. 根据权利要求6-9中任意一项所述的制备方法，其特征在于，所述助剂化合物选自含磷化合物和含铯化合物中的至少一种，优选自磷酸、氢氧化铯和硫酸铯中的至少一种。
  11. 一种SO2氧化制SO3的方法，包括：将包含SO2的气流与权利要求1-5中任意一项所述的催化剂或根据权利要求6-10中任意一项的制备方法所制备的催化剂接触，得到 包含SO3的气体产物。
PCT/CN2017/088011 2017-06-13 2017-06-13 一种钒基催化剂及其制备方法 Ceased WO2018227362A1 (zh)

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