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CN113600207A - Wide-temperature shift catalyst suitable for high CO and preparation and application thereof - Google Patents

Wide-temperature shift catalyst suitable for high CO and preparation and application thereof Download PDF

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CN113600207A
CN113600207A CN202111000036.6A CN202111000036A CN113600207A CN 113600207 A CN113600207 A CN 113600207A CN 202111000036 A CN202111000036 A CN 202111000036A CN 113600207 A CN113600207 A CN 113600207A
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CN113600207B (en
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严会成
许云波
欧军
孔德炜
刘阳
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Sichuan Shutai Chemical Technology Co ltd
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Sichuan Shutai Chemical Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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Abstract

The invention discloses a wide temperature shift catalyst suitable for high CO, and preparation and application thereof, belonging to the technical field of catalysts, in particular relating to the technical field of CO shift catalysts and solving the problems that the existing CO shift catalyst can not simultaneously meet the requirements of good low-temperature activity, wide use temperature range, good high-temperature thermal stability and low by-product, wherein the catalyst comprises 25-35 wt% of CuO, 25-40 wt% of ZnO, and Al2O3In an amount of 15 to 30 wt%, MnO2The content of (A) is 4-8 wt%, the content of CaO is 1-3 wt%, and Cs2The content of O is 0.3-0.5 wt%. The prepared Cu-series CO conversion catalyst has good low-temperature activity, wide use temperature range, good high-temperature thermal stability and low by-product, and is fit for the comprehensive utilization of the existing high-CO gas.

Description

Wide-temperature shift catalyst suitable for high CO and preparation and application thereof
Technical Field
The invention discloses a wide-temperature shift catalyst suitable for high CO, and preparation and application thereof, belongs to the technical field of catalysts, and particularly relates to the technical field of CO shift catalysts.
Background
In order to achieve the recycling economic targets of resource utilization maximization, "three wastes" zero discharge and "dry eating and squeezing out", a plurality of recycling projects of gases with high CO content (the CO content is more than or equal to 50%) appear in China at present, and a CO isothermal transformation process is mainly adopted and used for preparing methanol, synthetic ammonia and the like. In addition, in the hydrogen production by converting natural gas, the CO conversion tends to be a one-stage conversion in order to simplify the flow of the device. The two working conditions are that the inlet CO content of the conversion device is high, the temperature rise of the conversion bed layer is large, the temperature rise of the bed layer can reach 120-400 ℃, and the CO conversion catalyst needs to operate within the range of 200-400 ℃ for a long time. It is desirable that the shift catalyst have good activity at low temperatures and high reactivity and stability over a wide reaction range.
Currently, there are mainly 3 types of industrial CO shift catalysts: Fe-Cr series high temperature shift catalyst (300-. Among them, Fe-Cr series high-temperature shift catalyst is cheap, good in stability, but poor in low-temperature activity, has certain requirement for water-gas ratio (low water-gas ratio is easy to produce high by-product), and Cr2O3Is a highly toxic substance, is easy to cause harm to personnel and pollution to the environment in the processes of production, use and treatment. CuO/ZnO/Al2O3The catalyst is a low-temperature shift catalyst which has good low-temperature activity and can operate under the condition of low water-gas ratio, but has the problems that the crystal grain of the active component copper is easy to sinter, the thermal stability is poor and the like. The cobalt-molybdenum sulfur-resistant wide-temperature shift catalyst has the most outstanding advantages of strong sulfur resistance and toxicity resistance, wide use temperature range, high strength, long service life and the like, but has the defects of needing vulcanization before use, being complicated to operate, ensuring a certain sulfur content in raw materials in the use process, and otherwise being easy to desulfurize and deactivate.
It can be seen that these conventional catalysts are not suitable for the comprehensive utilization device of high-CO-content raw gas (raw gas does not contain S). In addition, when the traditional Cu-Zn-Al series CO transformation catalyst is applied in high CO gas, a methanol byproduct or a mixture with various structures is easily generated, and the selectivity of a target product is reduced.
Disclosure of Invention
The invention aims to: a high CO wide-temperature shift catalyst, a preparation method and an application thereof are provided to solve the problems that the existing CO shift catalyst can not simultaneously meet the requirements of good low-temperature activity, wide use temperature range, good high-temperature thermal stability and low by-product, and the existing CO shift catalyst is not suitable for a comprehensive utilization device of high CO content feed gas (the feed gas does not contain S).
The technical scheme adopted by the invention is as follows:
a catalyst suitable for high-CO shift in wide temp is prepared from CuO, ZnO and Al2O3，MnO2，CaO，Cs2O, wherein the content of CuO is 25-35 wt%, the content of ZnO is 25-40 wt%, and Al2O3In an amount of 15 to 30 wt%, MnO2The content of (A) is 4-8 wt%, the content of CaO is 1-3 wt%, and Cs2The content of O is 0.3-0.5 wt%
Preferably, the catalyst comprises CuO, ZnO, Al2O3，MnO2，CaO，Cs2O, wherein the content of CuO is 30 wt%, the content of ZnO is 36 wt%, and Al2O3Is 18 wt% MnO2Has a content of 6 wt%, a content of CaO of 2 wt%, and Cs2The O content was 0.4 wt%.
A preparation method of a wide temperature shift catalyst suitable for high CO comprises the following steps:
the method comprises the following steps:
step 1, calcining the pseudo-boehmite for 4-10h at the temperature of 850-2O3Then calcining the Al2O3Grinding to a particle size of more than 200 meshes to obtain Al2O3Powder is reserved;
step 2, adding Cu (NO)3)2、Zn(NO3)2、Mn(NO3)2The solution is prepared into mixed solution, and the metal in the mixed solutionThe total concentration of nitrate is 130-190g/L, and then prepared Al is added2O3Powder of Al2O3The ratio of the mass of the powder to the total mass of the metal salt in the mixed solution is 1.5-3: 13-19, stirring Al at a rotation speed of 300-450 rpm2O3Acidifying and dipping the powder for 1-2h to form mixed slurry, emulsifying the mixed slurry for 30-60min by using a three-stage emulsification pump, and heating the uniformly dispersed slurry of each phase to 80-90 ℃ under stirring to obtain mixed slurry for later use;
step 3, adding Na2CO3With NaHCO3The mixed alkali liquor and the mixture slurry are neutralized by high-speed collision of a centrifugal pump, the neutralization pH is 7.5-8.5, the neutralization temperature is 80-90 ℃, the neutralization time is 60-90min, after the neutralization is finished, the mixture is aged for 60-120min under the condition of 85-100 ℃, and the material is filtered and washed by a filter until Na in a filter cake2O is lower than 300mg/kg, then the washed filter cake is dried to the moisture content of the material within 5 percent by using a drying box, and finally the material is roasted for 2 to 4 hours in a calcining furnace at the temperature of 400-;
and 4, ball-milling the catalyst powder, the pure calcium aluminate cement, the cesium zincate and the graphite in a ball mill according to the mass ratio of 100: 8-10: 2-3: 1-2 until the particle sizes of the materials all pass through a 200-mesh sieve, then rolling and granulating the ball-milled mixed materials together with desalted water with the mass of 25-35%, drying the granulated materials until the water content is 5-10%, and pressing and forming the materials into a phi 5 x 5mm black cylinder to obtain the finished catalyst particles.
In the technical scheme of the application: mixed crystal phase (delta + theta) Al of pseudoboehmite calcined at high temperature2O3The catalyst carrier has the characteristics of high specific surface area and good stability, and the thermal stability of the catalyst carrier is obviously improved; mn can effectively improve the activity of the catalyst, the interaction of each component of the catalyst can be enhanced by adding Mn, particularly, the dispersion of the active component can be effectively promoted by forming a Cu-Mn compound, the sintering of the catalyst can be prevented, and the catalyst Mn not only can disperse the active component Cu on the surface of the catalyst, but also can prevent the crystal grain from growing up and plays a role of a structural catalyst promoter; cesium zincate has an obvious effect of inhibiting methanol productionThe generation of methanol in high CO gas is reduced; with Na2CO3With NaHCO3The mixed alkali liquor is neutralized by a high-speed centrifugal pump, the obtained material has good dispersibility of all components, the pore size distribution of the catalyst is concentrated (8-15nm), the generation of ineffective pores (2-5nm) is obviously reduced, the ineffective pores are easy to sinter, the structure of the catalyst is collapsed, the generation of pores is reduced, and the structural stability of the catalyst can be obviously improved; in the forming process of the catalyst, cement is added, which is beneficial to enhancing the physical strength of the catalyst, can obviously inhibit the crushing and pulverization of the catalyst in the using process, and can effectively stabilize the pore structure of the catalyst. According to the Cu-series CO conversion catalyst prepared by the application, due to the addition of Mn element and the adoption of the alumina carrier which is subjected to dipping heat treatment by using the metal liquid, the dispersibility of the active components of the catalyst is good, so that the catalyst has good catalytic activity at the temperature of 180-200 ℃; the catalyst carrier is subjected to heat treatment, the thermal stability is good, the pore distribution of the catalyst obtained by neutralizing with the mixed alkali liquor is more suitable for (8-15nm) catalytic reaction process, the pore structure is stable, the catalyst has good activity within the range of 200-400 ℃, and a wide use temperature zone is shown; and the addition of the cesium zincate auxiliary agent obviously reduces the methanol byproduct in the reaction process, and is in accordance with the recycling of the existing high CO gas.
Preferably, in step 1, the pseudoboehmite is calcined at 900 ℃ for 6 h.
Preferably, the mixed crystal phase Al in step 12O3The specific surface area of the alloy is more than or equal to 200m2/g。
Preferably, in step 2, Cu (NO) is contained in the mixed solution3)2Zn (NO) with a content of 60-80g/L3)2Mn (NO) in an amount of 60-90g/L3)2The content is 10-20 g/L.
Preferably, the rotating speed of the centrifugal pump in the step 3 is more than or equal to 2900 revolutions per minute.
Preferably, step 3 is Na2CO3With NaHCO3The mass ratio of the alkali liquor to the mixed alkali liquor is 2:8-8:2, and the total concentration of the mixed alkali liquor is 80-120 g/L.
More preferably, Na in step 32CO3With NaHCO3The mass ratio of (A) to (B) is 3:7-7: 3.
Preferably, step 3 is Na2CO3With NaHCO3The volume ratio of the mixed alkali liquor to the mixed slurry is 1.3-1.5: 1.
Preferably, the preparation of cesium zincate is carried out by mixing basic zinc carbonate, cesium carbonate and desalted water in a molar ratio of 1: 2: uniformly mixing the raw materials in a proportion of 10, and roasting the mixture for 2 to 4 hours at 400-500 ℃ to obtain the cesium zincate.
The application of the catalyst in high CO shift at the temperature of 180-400 ℃ is disclosed, wherein the volume ratio of water to CO is 1:1-6: 1.
In this application, CaO in pure calcium aluminate cement: al (Al)2O3＝25:75。
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the present invention, the mixed crystal phase (delta + theta) Al of pseudo-boehmite is calcined at high temperature2O3The catalyst carrier has the characteristics of high specific surface area and good stability, and the thermal stability of the catalyst carrier is obviously improved; mn can effectively improve the activity of the catalyst, the interaction of each component of the catalyst can be enhanced by adding Mn, particularly, the dispersion of the active component can be effectively promoted by forming a Cu-Mn compound, the sintering of the catalyst can be prevented, and the catalyst Mn not only can disperse the active component Cu on the surface of the catalyst, but also can prevent the crystal grain from growing up and plays a role of a structural catalyst promoter;
2. in the invention, due to the addition of Mn element and the adoption of the alumina carrier which is firstly dipped and heat-treated by metal liquid, the active component of the catalyst has good dispersibility, so that the catalyst has good catalytic activity at the temperature of 180-200 ℃;
3. in the invention, the catalyst carrier is subjected to heat treatment and has good thermal stability, the pore distribution of the catalyst obtained by neutralizing with the mixed alkali liquor is more suitable for (8-15nm) catalytic reaction process, the pore structure is stable, so that the catalyst has good activity within the range of 200-400 ℃, and a wide use temperature zone is shown;
4. according to the prepared Cu-series CO conversion catalyst, the auxiliary agent Mn is added, and the active component is subjected to a process of impregnation and then coprecipitation, so that the active component Cu is good in dispersibility, excellent low-temperature activity is shown, and the application temperature range is wide; the catalyst carrier is subjected to heat treatment, the thermal stability is good, the pore distribution of the catalyst obtained by neutralizing with the mixed alkali liquor is more suitable for (8-15nm) catalytic reaction process, the pore structure is stable, and the catalyst shows good thermal stability under the high-temperature condition of more than 300 ℃; the special cesium zincate auxiliary agent is added, so that the catalyst is low in by-product and good in selectivity, and the comprehensive utilization of the existing high-CO gas is conformed;
5. in the invention, the cesium zincate auxiliary agent is added, so that the methanol byproduct is obviously lower in the reaction process, and the recycling of the existing high CO gas is combined;
6. in the invention, cement is added in the catalyst in the forming process, which is beneficial to enhancing the physical strength of the catalyst, can obviously inhibit the crushing and pulverization of the catalyst in the using process, and can effectively stabilize the pore structure of the catalyst.
Drawings
FIG. 1 is a flow chart of the evaluation of the activity of the catalyst according to the present invention;
FIG. 2 is a graph showing the initial activity of samples according to various embodiments of the present invention;
FIG. 3 is a graph showing activity of samples according to various embodiments of the present invention after heat resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the catalyst suitable for high CO wide-temperature shift comprises the following steps:
step 1, preparing an alumina powder: calcining 200g of pseudo-boehmite at 850 ℃ for 10h to obtain Al with a mixed crystal phase (delta + theta)2O3Having a specific surface area of 220m2(ii)/g; then calcining the Al2O3Grinding until the granularity completely passes through 200 meshes for later use;
step 2, preparing mixture slurry: configuration 2000mL of Cu (NO)3)2、Zn(NO3)2、Mn(NO3)2The total concentration of metal nitrate in the mixed solution is 130g/L (Cu (NO) in the mixed solution)3)2Zn (NO) with a content of 60g/L3)2Mn (NO) in an amount of 60g/L3)2Content of 10g/L), and then Al obtained in the step 1 is added2O3Stirring 45g of powder at the rotating speed of 350 r/min, acidifying and soaking for 1h, emulsifying slurry for 60min by using a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 80 ℃ under stirring to obtain mixture slurry for later use;
step 3, preparing a neutralization alkali liquor: weighing 240gNa2CO3And 80g NaHCO3Dissolving in a proper amount of water to prepare 4000mL of mixed alkali liquor, wherein the concentration of the alkali liquor is 80g/L, and heating the alkali liquor to 80 ℃ for later use;
step 4, preparing materials: mixing Na2CO3With NaHCO3Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5: 1, performing high-speed collision neutralization, controlling the pH of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 80 ℃, the neutralization time to be 60min, and performing heat aging for 120min at 85 ℃ after the neutralization is finished; then the material is filtered and washed by a plate-frame filter until Na is contained in the material2The O content is lower than 300mg/kg, then the material is dried to the moisture content within 5 percent by using a spray drying or drying oven, and finally the material is roasted for 4 hours at the temperature of 400 ℃, thus obtaining catalyst powder;
step 5, cesium zincate preparation: adding basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1: 2: uniformly mixing the components in a ratio of 10, and roasting the mixture for 4 hours at 400 ℃ to obtain cesium zincate.
Step 6, catalyst preparation: ball-milling 200g of catalyst powder, 16g of pure calcium aluminate cement, 4g of cesium zincate and 2g of graphite in a 1L ball mill until the particle size of the mixed material completely passes through 200 meshes, adding 55.5g of desalted water, carrying out rolling granulation, drying until the material contains 5% of water, and carrying out compression molding to obtain a black cylinder with the diameter of phi 5 x 5mm, thus obtaining the finished catalyst particle.
Example 2
The preparation method of the catalyst suitable for high CO wide-temperature shift comprises the following steps:
step 1, preparing an alumina powder: calcining 200g of pseudo-boehmite at 1000 ℃ for 6h to obtain Al with a mixed crystal phase (delta + theta)2O3Having a specific surface area of 205m2(ii)/g; then calcining the Al2O3Grinding until the granularity completely passes through 300 meshes for later use;
step 2, preparing mixture slurry: configuration 2000mLCu (NO)3)2、Zn(NO3)2、Mn(NO3)2The total concentration of metal nitrate in the mixed solution is 190g/L (Cu (NO) in the mixed solution)3)2Zn (NO) with a content of 80g/L3)2Mn (NO) in an amount of 90g/L3)2Content of 20g/L), and then Al obtained in the step 1 is added2O3Acidifying and dipping 15g of powder for 2h, emulsifying the slurry for 60min by using a three-stage emulsification pump, and heating the uniformly dispersed slurry of each phase to 90 ℃ under stirring to obtain mixed slurry for later use;
step 3, preparing a neutralization alkali liquor: weighing 96gNa2CO3With 384g NaHCO3Dissolving in a proper amount of water to prepare 4000mL of mixed alkali liquor, wherein the concentration of the alkali liquor is 120g/L, and heating the alkali liquor to 90 ℃ for later use;
step 4, preparing materials: mixing Na2CO3With NaHCO3Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5: 1, performing high-speed collision neutralization, controlling the pH of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 90 ℃, the neutralization time to be 60min, and performing neutralization after the neutralization is finishedHeat aging at 100 deg.C for 90 min; then the material is filtered and washed by a plate-frame filter until Na is contained in the material2The O content is lower than 300mg/kg, then the material is dried to the moisture content within 5 percent by using a spray drying or drying oven, and finally the material is roasted for 2 hours at the temperature of 600 ℃, thus obtaining catalyst powder;
step 5, cesium zincate preparation: adding basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1: 2: uniformly mixing the components in a ratio of 10, and roasting the mixture for 2 hours at 500 ℃ to obtain cesium zincate.
Step 6, catalyst preparation: ball-milling 200g of catalyst powder, 20g of pure calcium aluminate cement, 6g of cesium zincate and 4g of graphite in a 1L ball mill until the particle size of the mixed material completely passes through 200 meshes, adding 69g of desalted water, carrying out rolling granulation, drying until the material contains 10% of water, and carrying out compression molding to obtain a black cylinder with the diameter of phi 5 multiplied by 5mm, namely the finished catalyst particle.
Example 3
The preparation method of the catalyst suitable for high CO wide-temperature shift comprises the following steps:
step 1, preparing an alumina powder: calcining 200g of pseudo-boehmite at 950 ℃ for 5h to obtain Al with a mixed crystal phase (delta + theta)2O3Having a specific surface area of 210m2(ii)/g; then calcining the Al2O3Grinding until the particle size of the mixture completely passes through 325 meshes for later use;
step 2, preparing mixture slurry: configuration 2000mLCu (NO)3)2、Zn(NO3)2、Mn(NO3)2The total concentration of metal nitrate in the mixed solution is 160g/L (Cu (NO) in the mixed solution)3)2Zn (NO) with a content of 70g/L3)2Mn (NO) in an amount of 75g/L3)2Content of 18g/L) and then Al obtained in the step 1 is added2O3Acidifying and dipping 35g of powder for 1.5h, emulsifying the slurry for 45min by using a three-stage emulsification pump, and heating the slurry with uniformly dispersed phases to 85 ℃ under stirring to obtain mixture slurry for later use;
step 3, preparing a neutralization alkali liquor: weighing 280g Na2CO3And 120g NaHCO3Dissolving in appropriate amount of water, and making into desired dosage form4000mL of mixed alkali liquor is obtained, the concentration of the alkali liquor is 100g/L, and the temperature of the alkali liquor is raised to 85 ℃ for standby;
step 4, preparing materials: mixing Na2CO3With NaHCO3Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5: 1, performing high-speed collision neutralization, controlling the pH of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 85 ℃, the neutralization time to be 80min, and performing heat aging for 100min at 85 ℃ after the neutralization is finished; then the material is filtered and washed by a plate-frame filter until Na is contained in the material2The O content is lower than 300mg/kg, then the material is dried to the moisture content within 5 percent by using a spray drying or drying oven, and finally the material is roasted for 3 hours at the temperature of 450 ℃, so that catalyst powder is obtained;
step 5, cesium zincate preparation: adding basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1: 2: uniformly mixing the components in a ratio of 10, and roasting the mixture for 3 hours at 450 ℃ to obtain cesium zincate.
Step 6, catalyst preparation: ball-milling 200g of catalyst powder, 18g of pure calcium aluminate cement, 5g of cesium zincate and 3g of graphite in a 1L ball mill until the particle size of the mixed material completely passes through 200 meshes, adding 61g of desalted water, carrying out rolling granulation, drying until the material contains 6.5% of water, and carrying out compression molding to obtain a black cylinder with the diameter of phi 5 multiplied by 5mm, namely the finished catalyst particle.
Example 4
The preparation method of the catalyst suitable for high CO wide-temperature shift comprises the following steps:
step 1, preparing an alumina powder: calcining 100g of pseudo-boehmite at 900 ℃ for 6h to obtain Al with a mixed crystal phase (delta + theta)2O3Having a specific surface area of 213m2(ii)/g; then calcining the Al2O3Grinding until the granularity completely passes through 250 meshes for later use;
step 2, preparing mixture slurry: configuration 2000mLCu (NO)3)2、Zn(NO3)2、Mn(NO3)2The total concentration of metal nitrate in the mixed solution is 160g/L (Cu (NO) in the mixed solution)3)2Zn (NO) with a content of 70g/L3)2Mn (NO) in an amount of 80g/L3)2Content of 15g/L) and then Al obtained in the step 1 is added2O3Acidifying and soaking 23g of powder for 1.5h, emulsifying the slurry for 45min by using a three-stage emulsification pump, and heating the uniformly dispersed slurry of each phase to 83 ℃ under stirring to obtain mixture slurry for later use;
step 3, preparing a neutralization alkali liquor: weighing 200g of Na2CO3And 200g NaHCO3Dissolving in a proper amount of water to prepare 4000mL of mixed alkali liquor, wherein the concentration of the alkali liquor is 100g/L, and heating the alkali liquor to 83 ℃ for later use;
step 4, preparing materials: mixing Na2CO3With NaHCO3Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5: 1, performing high-speed collision neutralization, controlling the pH of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 83 ℃, the neutralization time to be 75min, and performing thermal aging for 80min at the temperature of 90 ℃ after the neutralization is finished; then the material is filtered and washed by a plate-frame filter until Na is contained in the material2The O content is lower than 300mg/kg, then the material is dried to the moisture content within 5 percent by using a spray drying or drying oven, and finally the material is roasted for 3 hours at the temperature of 450 ℃, so that catalyst powder is obtained;
step 5, cesium zincate preparation: adding basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1: 2: uniformly mixing the components in a ratio of 10, and roasting the mixture for 3 hours at 450 ℃ to obtain cesium zincate.
Step 6, catalyst preparation: ball-milling 200g of catalyst powder, 20g of pure calcium aluminate cement, 4g of cesium zincate and 3g of graphite in a 1L ball mill until the particle size of the mixed material completely passes through 200 meshes, adding 68g of desalted water, carrying out rolling granulation, drying until the material contains 8% of water, and carrying out compression molding to obtain a black cylinder with the diameter of phi 5 multiplied by 5mm, namely the finished catalyst particle.
Example 5
A preparation method of a cesium-free catalyst suitable for CO wide-temperature shift comprises the following steps:
step 1, preparing an alumina powder: calcining 100g of pseudo-boehmite at 900 ℃ for 6h to obtain Al with a mixed crystal phase (delta + theta)2O3Having a specific surface area of 213m2(ii)/g; then calcining the Al2O3Grinding to particle sizePassing through 250 meshes for later use;
step 2, preparing mixture slurry: configuration 2000mLCu (NO)3)2、Zn(NO3)2、Mn(NO3)2The total concentration of metal nitrate in the mixed solution is 160g/L (Cu (NO) in the mixed solution)3)2Zn (NO) with a content of 70g/L3)2Mn (NO) in an amount of 80g/L3)2Content of 15g/L) and then Al obtained in the step 1 is added2O3Acidifying and soaking 23g of powder for 1.5h, emulsifying the slurry for 45min by using a three-stage emulsification pump, and heating the uniformly dispersed slurry of each phase to 83 ℃ under stirring to obtain mixture slurry for later use;
step 3, preparing a neutralization alkali liquor: weighing 200g of Na2CO3And 200g NaHCO3Dissolving in a proper amount of water to prepare 4000mL of mixed alkali liquor, wherein the concentration of the alkali liquor is 100g/L, and heating the alkali liquor to 83 ℃ for later use;
step 4, preparing materials: mixing Na2CO3With NaHCO3Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5: 1, performing high-speed collision neutralization, controlling the pH of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 83 ℃, the neutralization time to be 75min, and performing thermal aging for 80min at the temperature of 90 ℃ after the neutralization is finished; then the material is filtered and washed by a plate-frame filter until Na is contained in the material2The O content is lower than 300mg/kg, then the material is dried to the moisture content within 5 percent by using a spray drying or drying oven, and finally the material is roasted for 3 hours at the temperature of 450 ℃, so that catalyst powder is obtained;
step 5, catalyst preparation: ball-milling 200g of catalyst powder, 20g of pure calcium aluminate cement and 3g of graphite in a 1L ball mill until the particle size of the mixture completely passes through 200 meshes, adding 68g of desalted water, rolling and granulating, drying until the water content of the material is 8%, and pressing and forming into a black cylinder with the diameter of 5 x 5mm, namely the finished catalyst particle.
Test examples
Catalyst Activity test contrast
FIG. 1 shows an apparatus for evaluating the activity of a catalyst, in which a catalyst having a primary particle size (. PHI.5X 5mm particle size) is first charged into an isothermal zone of a reactor30mL of pellets, then according to the catalyst activation in Table 1 used H2-N2Activation is required for 18h at 230 ℃; then, the reaction mixture was switched to the raw material gas for detection in Table 1 and was changed to H2Desalted water was metered in with an O/CO volume ratio of 1.5, the internal temperature of the vaporizer was controlled at 250 ℃ and the reactor was tested as per the test requirements in Table 2.
The performance of the catalyst prepared in the above example (wherein example 5 is a preparation method of cesium-free catalyst suitable for wide temperature shift of CO) was tested, the test apparatus is shown in fig. 1, the composition of the raw material gas is shown in table 1 below, and the test conditions are shown in table 2 below:
table 1 feed gas composition v%
Figure BDA0003233088080000101
Figure BDA0003233088080000111
TABLE 2 test conditions
Figure BDA0003233088080000112
The catalyst activity test results are shown in fig. 2 and fig. 3:
FIG. 2 shows the initial activity of the catalysts of the examples;
FIG. 3 shows activity of the catalysts of the examples after heat resistance;
the test results in FIG. 2 show that the catalysts in examples 1-5 have CO conversion rates higher than 80% at 200-400 ℃, and have good initial activity;
the test results in FIG. 3 show that the catalysts in examples 1-5 have CO conversion rate still higher than 75% at 200-400 ℃ after heat resistance, have good activity after heat resistance, and show good thermal stability;
table 3 comparison of methanol content in tail gas at 250 ℃ for catalysts of examples
Figure BDA0003233088080000113
As shown in Table 3, the addition of cesium zincate promoter in examples 1-4 resulted in a significantly lower methanol byproduct during the reaction, whereas the addition of cesium zincate promoter in example 5 resulted in a significantly higher methanol byproduct than in examples 1-4, which resulted in a significantly higher effective CO utilization.

Claims (10)

1. A wide temperature shift catalyst suitable for high CO, characterized in that the catalyst comprises CuO, ZnO, Al2O3，MnO2，CaO，Cs2O, wherein the content of CuO is 25-35 wt%, the content of ZnO is 25-40 wt%, and Al2O3In an amount of 15 to 30 wt%, MnO2The content of (A) is 4-8 wt%, the content of CaO is 1-3 wt%, and Cs2The content of O is 0.3-0.5 wt%.
2. A method for preparing a wide temperature shift catalyst suitable for high CO according to claim 1, comprising the steps of:
step 1, calcining the pseudo-boehmite for 4-10h at the temperature of 850-2O3Then calcining the Al2O3Grinding to a particle size of more than 200 meshes to obtain Al2O3Powder is reserved;
step 2, adding Cu (NO)3)2、Zn(NO3)2、Mn(NO3)2The solution is prepared into mixed solution, the total concentration of metal nitrate in the mixed solution is 130-190g/L, and then the prepared Al is added2O3Powder of Al2O3The ratio of the mass of the powder to the total mass of the metal salt in the mixed solution is 1.5-3: 13-19, stirring Al at a rotation speed of 300-450 rpm2O3Acidifying and soaking the powder for 1-2h to form mixed slurry, emulsifying the mixed slurry for 30-60min with a three-stage emulsification pump, heating the uniformly dispersed slurry to 80-90 deg.C under stirring to obtain mixed slurryStandby;
step 3, adding Na2CO3With NaHCO3The mixed alkali liquor and the mixture slurry are neutralized by high-speed collision of a centrifugal pump, the neutralization pH is 7.5-8.5, the neutralization temperature is 80-90 ℃, the neutralization time is 60-90min, after the neutralization is finished, the mixture is aged for 60-120min under the condition of 85-100 ℃, and the material is filtered and washed by a filter until Na in a filter cake2O is lower than 300mg/kg, then the washed filter cake is dried to the moisture content of the material within 5 percent by using a drying box, and finally the material is roasted for 2 to 4 hours in a calcining furnace at the temperature of 400-;
and 4, ball-milling the catalyst powder, the pure calcium aluminate cement, the cesium zincate and the graphite in a ball mill according to the mass ratio of 100: 8-10: 2-3: 1-2 until the particle sizes of the materials all pass through a 200-mesh sieve, then rolling and granulating the ball-milled mixed materials together with desalted water with the mass of 25-35%, drying the granulated materials until the water content is 5-10%, and pressing and forming the materials into a phi 5 x 5mm black cylinder to obtain the finished catalyst particles.
3. The method of claim 2, wherein the catalyst is prepared by the following steps: in step 1, the pseudo-boehmite is calcined for 6h at 900 ℃.
4. The method of claim 2, wherein the catalyst is prepared by the following steps: mixed crystal phase Al in step 12O3The specific surface area of the alloy is more than or equal to 200m2/g。
5. The method of claim 2, wherein the catalyst is prepared by the following steps: in step 2, Cu (NO) is present in the mixed solution3)2Zn (NO) with a content of 60-80g/L3)2Mn (NO) in an amount of 60-90g/L3)2The content is 10-20 g/L.
6. The method of claim 2, wherein the catalyst is used in the wide temperature shift process for high COCharacterized in that: in step 3 Na2CO3With NaHCO3The mass ratio of the alkali liquor to the mixed alkali liquor is 2:8-8:2, and the total concentration of the mixed alkali liquor is 80-120 g/L.
7. The method of claim 6, wherein the catalyst is prepared by the following steps: in step 3 Na2CO3With NaHCO3The mass ratio of (A) to (B) is 3:7-7: 3.
8. The method of claim 2, wherein the catalyst is prepared by the following steps: in step 3 Na2CO3With NaHCO3The volume ratio of the mixed alkali liquor to the mixed slurry is 1.3-1.5: 1.
9. The method of claim 2, wherein the catalyst is prepared by the following steps: preparing cesium zincate by mixing basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1: 2: uniformly mixing the raw materials in a proportion of 10, and roasting the mixture for 2 to 4 hours at 400-500 ℃ to obtain the cesium zincate.
10. Use of a wide temperature shift catalyst suitable for high CO according to claim 1 wherein: the catalyst is applied to high CO shift in a temperature range of 180 ℃ and 400 ℃, wherein the volume ratio of water to CO is 1:1-6: 1.
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