CN113600207B - Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof - Google Patents
Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof Download PDFInfo
- Publication number
- CN113600207B CN113600207B CN202111000036.6A CN202111000036A CN113600207B CN 113600207 B CN113600207 B CN 113600207B CN 202111000036 A CN202111000036 A CN 202111000036A CN 113600207 B CN113600207 B CN 113600207B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mixed
- content
- neutralization
- wide temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J23/002—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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
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, so as to solve the problems that the existing CO shift catalyst cannot simultaneously meet the requirements of good low-temperature activity, wide use temperature range, good high-temperature stability and low byproduct, wherein the catalyst comprises 25-35wt% of CuO, 25-40wt% of ZnO and Al 2 O 3 The content of (C) is 15-30wt%, mnO 2 4-8wt% of CaO, 1-3wt% of Cs 2 The content of O is 0.3-0.5wt%. The prepared Cu-series CO conversion catalyst has good low-temperature activity, wide use temperature range, good high-temperature stability and low byproducts, and is suitable for the comprehensive utilization of the existing high-CO gas.
Description
Technical Field
The invention discloses a wide-temperature shift catalyst applicable to 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 cyclic economic targets of maximizing resource utilization, zero emission of three wastes and complete eating, drying and squeezing, more recycling projects of high-CO-content gas (CO content is more than or equal to 50%) appear in China at present, and a CO isothermal conversion process is mainly adopted for preparing methanol, synthetic ammonia and the like. In addition, in the hydrogen production by natural gas conversion, the CO conversion tends to be one-stage conversion in order to simplify the device flow. Both 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 120-200 ℃, and the CO conversion catalyst is required to operate within the range of 200-400 ℃ for a long time. This requires a shift catalyst having good activity at low temperatures, and at the same time having high reactivity and stability in a wide reaction zone.
Currently, the industrialized CO shift catalysts mainly have 3 types: fe-Cr high temperature shift catalyst (300-500 ℃), cu-Zn-Al low temperature shift catalyst (190-250 ℃) and Co-Mo sulfur-resistant shift catalyst (180-450 ℃). Wherein, the Fe-Cr series high temperature shift catalyst has low price and good stability, but has poor low temperature activity, certain requirement on the water-gas ratio (high byproducts are easy to appear when the water-gas ratio is low), and Cr 2 O 3 Is a highly toxic substance, and is easy to cause injury to personnel and environmental pollution in the production, use and treatment processes. CuO/ZnO/Al 2 O 3 The catalyst is a low-temperature shift catalyst, has good low-temperature activity and can operate under the condition of low water-gas ratio, but has the problems that copper crystal grains as an active component are easy to sinter, the thermal stability is poor, and the like. The cobalt-molybdenum sulfur-resistant wide-temperature conversion catalyst has the most outstanding advantages of strong sulfur resistance and poison resistance, wide use temperature range, high strength, long service life and the like, but has the defects of vulcanization before use, complex operation, certain sulfur content in raw materials in the use process, or the catalyst is easy to be reversely vulcanized and deactivated.
It can be seen that these conventional catalysts are not suitable for comprehensive utilization devices of feed gas with high CO content (no S in the feed gas). In addition, the use of conventional Cu-Zn-Al based CO shift catalysts in high CO gas is prone to produce methanol by-products or various structured mixtures, which will reduce the selectivity of the target product.
Disclosure of Invention
The invention aims at: a high-CO wide-temperature shift catalyst and preparation and application thereof are provided, which solves 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 stability and low byproducts, and is not applicable to a comprehensive utilization device of high-CO content raw material gas (the raw material gas contains no S).
The technical scheme adopted by the invention is as follows:
wide temperature range suitable for high COChanging catalyst, the catalyst comprises CuO, znO and Al 2 O 3 ，MnO 2 ，CaO，Cs 2 O, wherein the content of CuO is 25-35wt%, the content of ZnO is 25-40wt%, al 2 O 3 The content of (C) is 15-30wt%, mnO 2 4-8wt% of CaO, 1-3wt% of Cs 2 The content of O is 0.3-0.5wt%
Preferably, the catalyst comprises CuO, znO and Al 2 O 3 ，MnO 2 ，CaO，Cs 2 O, wherein the content of CuO is 30wt%, the content of ZnO is 36wt%, al 2 O 3 The content of (C) is 18wt%, mnO 2 The content of (2) was 6wt%, the content of CaO was 2wt%, cs 2 The O content was 0.4wt%.
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 pseudo-boehmite for 4-10 hours at 850-1000 ℃ to obtain mixed crystal phase (delta+theta) Al with good thermal stability and larger specific surface area 2 O 3 Then calcined Al 2 O 3 Grinding to above 200 mesh to obtain Al 2 O 3 Powder is reserved for standby;
step 2, cu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 Preparing a mixed solution with the total concentration of metal nitrate of 130-190g/L, and adding prepared Al 2 O 3 Powder, al 2 O 3 The ratio of the mass of the powder to the total mass of the metal salt in the mixed solution is 1.5-3: 13 to 19, and Al is added under the condition of stirring rotation speed of 300 to 450 revolutions per minute 2 O 3 Acidifying and impregnating the powder for 1-2h to form mixed slurry, emulsifying the mixed slurry for 30-60min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 80-90 ℃ under stirring to obtain mixed slurry liquid for later use;
step 3, na is carried out 2 CO 3 With NaHCO 3 The mixed alkali liquor and the mixed slurry are subjected to high-speed collision neutralization by a centrifugal pump, the neutralization pH is 7.5-8.5, and the neutralization temperature isHeat aging at 80-90deg.C for 60-90min for 60-120min at 85-100deg.C, filtering, washing with filter to obtain Na in filter cake 2 O is lower than 300mg/kg, then the washed filter cake is dried to the moisture content of less than 5% by a drying box, and finally the catalyst powder is obtained by roasting for 2-4 hours in a calciner at 400-600 ℃;
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 size is all passed through a 200-mesh sieve, rolling the ball-milled mixed material and desalted water with the mass of 25-35%, granulating, and when the water content of the granulated material is 5-10%, pressing the material into phi 5X 5mm black cylinders, thus obtaining the finished catalyst particles.
In the technical scheme of the application: mixed crystal phase (delta + theta) Al of pseudo-boehmite calcined at high temperature 2 O 3 The catalyst 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 addition of Mn can enhance the interaction of the components of the catalyst, particularly the formation of Cu-Mn complex can effectively promote the dispersion of active components and prevent the sintering of the catalyst, and the Mn of the catalyst can not only disperse more active component Cu on the surface of the catalyst, but also prevent the growth of crystal grains of the catalyst and play the role of a structural promoter; cesium zincate has the effect of inhibiting the production of methanol, and obviously reduces the production of methanol in high CO gas; with Na 2 CO 3 With NaHCO 3 The mixed alkali liquor is neutralized, and a high-speed centrifugal pump is used for neutralization, so that the dispersibility of each component in the obtained material is good, the pore size distribution of the catalyst is concentrated (8-15 nm), the generation of invalid pores (2-5 nm) is obviously reduced, the invalid pores are easy to sinter, the catalyst structure is collapsed, the generation of pores is reduced, and the stability of the catalyst structure can be obviously increased; the cement is added in the catalyst in the molding process, so that the physical strength of the catalyst is enhanced, the crushing and pulverization of the catalyst in the use process can be obviously inhibited, and the pore structure of the catalyst can be effectively stabilized. The Cu-based CO conversion catalyst prepared by the application adopts the prior metal due to the addition of Mn elementThe alumina carrier treated by liquid impregnation and heat treatment has good dispersibility of active components of the catalyst, so that the catalyst has good catalytic activity at 180-200 ℃; the catalyst carrier is subjected to heat treatment, the heat stability is good, the pore distribution of the catalyst obtained by adding mixed alkali liquor for neutralization is more suitable (8-15 nm) in the catalytic reaction process, the pore structure is stable, so that the catalyst has good activity in the range of 200-400 ℃, and a wide use temperature zone is shown; the cesium zincate auxiliary agent is added, the methanol byproduct is obviously lower in the reaction process, and the recycling of the existing high-CO gas is compatible.
Preferably, in step 1, pseudo-boehmite is calcined at 900 ℃ for 6 hours.
Preferably, in step 1, al is mixed in a crystalline phase 2 O 3 The specific surface area of (2) is more than or equal to 200m 2 /g。
Preferably, in step 2, cu (NO 3 ) 2 The content of Zn (NO) is 60-80g/L 3 ) 2 The content is 60-90g/L, mn (NO) 3 ) 2 The content is 10-20g/L.
Preferably, the rotating speed of the centrifugal pump in the step 3 is more than or equal to 2900 rpm.
Preferably, na in step 3 2 CO 3 With NaHCO 3 The mass ratio of the alkali solution to the mixed alkali solution is 2:8-8:2, and the total concentration of the mixed alkali solution is 80-120g/L.
More preferably, na in step 3 2 CO 3 With NaHCO 3 The mass ratio of (3:7) to (7:3).
Preferably, na in step 3 2 CO 3 With NaHCO 3 The volume ratio of the mixed alkali liquor to the mixed slurry is 1.3-1.5:1.
Preferably, cesium zincate is prepared by mixing basic zinc carbonate, cesium carbonate and desalted water according to a molar ratio of 1:2: mixing the materials in a proportion of 10 uniformly, and roasting the mixture at 400-500 ℃ for 2-4 hours to obtain cesium zincate.
The application of a wide temperature shift catalyst suitable for high CO is disclosed, wherein the catalyst is applied to high CO shift in a temperature range of 180-400 ℃, and the volume ratio of water to CO is 1:1-6:1.
In this application, caO in pure calcium aluminate cement: al (Al) 2 O 3 ＝25:75。
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. in the invention, the pseudo-boehmite is calcined at high temperature into mixed crystal phase (delta+theta) Al 2 O 3 The catalyst 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 addition of Mn can enhance the interaction of the components of the catalyst, particularly the formation of Cu-Mn complex can effectively promote the dispersion of active components and prevent the sintering of the catalyst, and the Mn of the catalyst can not only disperse more active component Cu on the surface of the catalyst, but also prevent the growth of crystal grains of the catalyst and play the role of a structural promoter;
2. in the invention, as Mn element is added and the alumina carrier which is heat treated by dipping with metal liquid is adopted, the dispersibility of the active component of the catalyst is good, so that the catalyst has good catalytic activity at 180-200 ℃;
3. in the invention, the catalyst carrier is subjected to heat treatment, the heat stability is good, the pore distribution of the catalyst obtained by adding mixed alkali liquor for neutralization is more suitable (8-15 nm) in the catalytic reaction process, the pore structure is stable, the catalyst has good activity in the range of 200-400 ℃, and a wide use temperature zone is shown;
4. the prepared Cu-series CO conversion catalyst is added with an auxiliary agent Mn and an active component is subjected to a process of dipping and then coprecipitation, so that the active component Cu has good dispersibility, shows excellent low-temperature activity and has a wide use temperature range; the catalyst carrier is subjected to heat treatment, has good heat stability, and the pore distribution of the catalyst obtained by adding mixed alkali liquor for neutralization is more suitable (8-15 nm) in the catalytic reaction process, has stable pore structure and shows good heat stability at the high temperature of more than 300 ℃; the special cesium zincate auxiliary agent is added, so that the catalyst has low byproducts and good selectivity, and is compatible with the comprehensive utilization of the existing high-CO gas;
5. in the invention, the cesium zincate auxiliary agent is added, the methanol byproduct is obviously lower in the reaction process, and the recycling of the existing high CO gas is compatible;
6. in the invention, cement is added in the catalyst in the molding process, so that the physical strength of the catalyst is enhanced, the crushing and pulverization of the catalyst in the use process can be obviously inhibited, and the pore structure of the catalyst can be effectively stabilized.
Drawings
FIG. 1 is a flow chart of the catalyst activity evaluation of the present invention;
FIG. 2 shows the primary activity of samples according to various embodiments of the present invention;
FIG. 3 shows the activity of samples of various embodiments of the present invention after heat resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the 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 invention, as 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 made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the catalyst suitable for high CO wide temperature range conversion comprises the following steps:
step 1, preparing alumina powder: calcining 200g pseudo-boehmite at 850 ℃ for 10 hours to obtain Al with mixed crystal phase (delta+theta) 2 O 3 Its specific surface area is 220m 2 /g; then calcined Al 2 O 3 Grinding until the granularity of the powder passes through 200 meshes for standby;
step 2, preparing mixed slurry: 2000mL Cu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 Mixed solution of metal nitrateThe concentration was 130g/L (Cu (NO) 3 ) 2 The content of Zn (NO) is 60g/L 3 ) 2 The content of Mn (NO) is 60g/L 3 ) 2 The content is 10 g/L), and then Al obtained in the step 1 is added 2 O 3 45g of powder, acidifying and dipping for 1h under the stirring condition of the rotating speed of 350 r/min, emulsifying the slurry for 60min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 80 ℃ under the stirring after the emulsification to obtain mixed slurry for standby;
step 3, preparing a neutralization alkali liquor: weigh 240g Na 2 CO 3 And 80g NaHCO 3 Dissolving in a proper amount of water, preparing 4000mL of mixed alkali liquor with the alkali liquor concentration of 80g/L, and heating the alkali liquor to 80 ℃ for standby;
step 4, material preparation: na is mixed with 2 CO 3 With NaHCO 3 Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5:1, carrying out high-speed collision neutralization, controlling the pH value 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 carrying out heat aging for 120min at the temperature of 85 ℃ after the neutralization is finished; then filtering and washing the materials by a plate-and-frame filter until Na in the materials 2 The O content is lower than 300mg/kg, then the material moisture is dried to be within 5% by a spray drying or drying box, and finally the catalyst powder is obtained after roasting for 4 hours at 400 ℃;
step 5, cesium zincate preparation: basic zinc carbonate, cesium carbonate and desalted water are mixed according to a mole ratio of 1:2: mixing evenly in proportion of 10, and roasting for 4 hours at 400 ℃ to obtain cesium zincate.
Step 6, preparing a catalyst: 200g of catalyst powder, 16g of pure calcium aluminate cement, 4g of cesium zincate and 2g of graphite are taken, the mixture is ball-milled in a 1L ball mill until the granularity of the mixture passes through 200 meshes, then 55.5g of desalted water is added for rolling and granulating, the mixture is dried until the water content of the mixture is 5%, and the mixture is pressed into a phi 5 multiplied by 5mm black cylinder, thus obtaining the finished catalyst particles.
Example 2
The preparation method of the catalyst suitable for high CO wide temperature range conversion comprises the following steps:
step 1, preparing alumina powder: 200g of pseudo-boehmite is taken at 1000 DEG CCalcining for 6h under the condition to obtain the Al with mixed crystal phase (delta+theta) 2 O 3 Its specific surface area is 205m 2 /g; then calcined Al 2 O 3 Grinding until the granularity of the powder completely passes 300 meshes for standby;
step 2, preparing mixed slurry: configuration 2000mLCu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 A mixed solution in which the total concentration of metal nitrate in the mixed solution was 190g/L (Cu (NO in the mixed solution 3 ) 2 The content of Zn (NO) is 80g/L 3 ) 2 The content of Mn (NO) is 90g/L 3 ) 2 The content is 20 g/L), and then Al obtained in the step 1 is added 2 O 3 15g of powder, acidifying and impregnating for 2h, emulsifying the slurry for 60min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 90 ℃ under stirring to obtain mixed slurry for later use;
step 3, preparing a neutralization alkali liquor: weigh 96g Na 2 CO 3 And 384g NaHCO 3 Dissolving in a proper amount of water, preparing 4000mL of mixed alkali liquor with the concentration of 120g/L, and heating the alkali liquor to 90 ℃ for standby;
step 4, material preparation: na is mixed with 2 CO 3 With NaHCO 3 Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5:1, carrying out high-speed collision neutralization, controlling the pH value of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 90 ℃, the neutralization time to be 60 minutes, and carrying out heat aging for 90 minutes at the temperature of 100 ℃ after the neutralization is finished; then filtering and washing the materials by a plate-and-frame filter until Na in the materials 2 The O content is lower than 300mg/kg, then the material moisture is dried to be within 5% by a spray drying or drying box, and finally the catalyst powder is obtained after roasting for 2 hours at 600 ℃;
step 5, cesium zincate preparation: basic zinc carbonate, cesium carbonate and desalted water are mixed according to a mole ratio of 1:2: mixing evenly in proportion of 10, and roasting for 2 hours at 500 ℃ to obtain cesium zincate.
Step 6, preparing a catalyst: 200g of catalyst powder, 20g of pure calcium aluminate cement, 6g of cesium zincate and 4g of graphite are taken, the mixture is ball-milled in a 1L ball mill until the granularity of the mixture passes through 200 meshes, 69g of desalted water is added for rolling and granulating, the mixture is dried until the water content of the mixture is 10%, and the mixture is pressed into a phi 5 multiplied by 5mm black cylinder, thus obtaining the finished catalyst particles.
Example 3
The preparation method of the catalyst suitable for high CO wide temperature range conversion comprises the following steps:
step 1, preparing alumina powder: calcining 200g pseudo-boehmite at 950 ℃ for 5h to obtain Al with mixed crystal phase (delta+theta) 2 O 3 Its specific surface area is 210m 2 /g; then calcined Al 2 O 3 Grinding until the granularity passes 325 meshes for standby;
step 2, preparing mixed slurry: configuration 2000mLCu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 A mixed solution in which the total concentration of metal nitrate in the mixed solution was 160g/L (Cu (NO in the mixed solution 3 ) 2 The content of Zn (NO) is 70g/L 3 ) 2 The content of Mn (NO) is 75g/L 3 ) 2 The content is 18 g/L), and then Al obtained in the step 1 is added 2 O 3 35g of powder, acidifying and impregnating for 1.5h, emulsifying the slurry for 45min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 85 ℃ under stirring to obtain mixed slurry for later use;
step 3, preparing a neutralization alkali liquor: weigh 280gNa 2 CO 3 And 120g NaHCO 3 Dissolving in a proper amount of water, preparing 4000mL of mixed alkali liquor with the concentration of 100g/L, and heating the alkali liquor to 85 ℃ for standby;
step 4, material preparation: na is mixed with 2 CO 3 With NaHCO 3 Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5:1, carrying out high-speed collision neutralization, controlling the pH value of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 85 ℃, the neutralization time to be 80 minutes, and carrying out heat aging for 100 minutes at the temperature of 85 ℃ after the neutralization is finished; then filtering and washing the materials by a plate-and-frame filter until Na in the materials 2 The O content is lower than 300mg/kg, then the material moisture is dried to be within 5% by a spray drying or drying box, and finally the catalyst powder is obtained by roasting for 3 hours at 450 ℃;
step 5, cesium zincate preparation: basic zinc carbonate, cesium carbonate and desalted water are mixed according to a mole ratio of 1:2: mixing uniformly in 10 proportion, and roasting at 450 ℃ for 3 hours to obtain cesium zincate.
Step 6, preparing a catalyst: 200g of catalyst powder, 18g of pure calcium aluminate cement, 5g of cesium zincate and 3g of graphite are taken, the mixture is ball-milled in a 1L ball mill until the granularity of the mixture passes through 200 meshes, 61g of desalted water is added for rolling and granulating, the mixture is dried until the water content of the mixture is 6.5%, and the mixture is pressed into a phi 5 multiplied by 5mm black cylinder, thus obtaining the finished catalyst particles.
Example 4
The preparation method of the catalyst suitable for high CO wide temperature range conversion comprises the following steps:
step 1, preparing alumina powder: calcining 100g pseudo-boehmite at 900 ℃ for 6h to obtain Al with mixed crystal phase (delta+theta) 2 O 3 Its specific surface area is 213m 2 /g; then calcined Al 2 O 3 Grinding until the granularity completely passes through 250 meshes for standby;
step 2, preparing mixed slurry: configuration 2000mLCu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 A mixed solution in which the total concentration of metal nitrate in the mixed solution was 160g/L (Cu (NO in the mixed solution 3 ) 2 The content of Zn (NO) is 70g/L 3 ) 2 The content of Mn (NO) is 80g/L 3 ) 2 15 g/L), and then adding Al obtained in the step 1 2 O 3 23g of powder, acidizing and immersing for 1.5h, emulsifying the slurry for 45min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 83 ℃ under stirring after emulsification to obtain mixed slurry for later use;
step 3, preparing a neutralization alkali liquor: weigh 200gNa 2 CO 3 And 200g NaHCO 3 Dissolving in a proper amount of water, preparing 4000mL of mixed alkali liquor with the concentration of 100g/L, and heating the alkali liquor to 83 ℃ for standby;
step 4, material preparation: na is mixed with 2 CO 3 With NaHCO 3 The mixed alkali liquor and the mixed metal liquor are added according to the volume ratio of 1.3-1.5:1High-speed collision neutralization in a centrifugal pump, controlling the pH value 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 after the neutralization is finished, carrying out heat aging for 80min at 90 ℃; then filtering and washing the materials by a plate-and-frame filter until Na in the materials 2 The O content is lower than 300mg/kg, then the material moisture is dried to be within 5% by a spray drying or drying box, and finally the catalyst powder is obtained by roasting for 3 hours at 450 ℃;
step 5, cesium zincate preparation: basic zinc carbonate, cesium carbonate and desalted water are mixed according to a mole ratio of 1:2: mixing uniformly in 10 proportion, and roasting at 450 ℃ for 3 hours to obtain cesium zincate.
Step 6, preparing a catalyst: 200g of catalyst powder, 20g of pure calcium aluminate cement, 4g of cesium zincate and 3g of graphite are taken, the mixture is ball-milled in a 1L ball mill until the granularity of the mixture passes through 200 meshes, 68g of desalted water is added for rolling and granulating, the mixture is dried until the water content of the mixture is 8%, and the mixture is pressed into a phi 5 multiplied by 5mm black cylinder, thus obtaining the finished catalyst particles.
Example 5
A preparation method of a cesium-free catalyst suitable for wide temperature range CO transformation, comprising the following steps:
step 1, preparing alumina powder: calcining 100g pseudo-boehmite at 900 ℃ for 6h to obtain Al with mixed crystal phase (delta+theta) 2 O 3 Its specific surface area is 213m 2 /g; then calcined Al 2 O 3 Grinding until the granularity completely passes through 250 meshes for standby;
step 2, preparing mixed slurry: configuration 2000mLCu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 A mixed solution in which the total concentration of metal nitrate in the mixed solution was 160g/L (Cu (NO in the mixed solution 3 ) 2 The content of Zn (NO) is 70g/L 3 ) 2 The content of Mn (NO) is 80g/L 3 ) 2 15 g/L), and then adding Al obtained in the step 1 2 O 3 23g of powder, acidizing and immersing for 1.5h, emulsifying the slurry for 45min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 83 ℃ under stirring after emulsification to obtain mixed slurry for later use;
step 3, preparing a neutralization alkali liquor: weigh 200gNa 2 CO 3 And 200g NaHCO 3 Dissolving in a proper amount of water, preparing 4000mL of mixed alkali liquor with the concentration of 100g/L, and heating the alkali liquor to 83 ℃ for standby;
step 4, material preparation: na is mixed with 2 CO 3 With NaHCO 3 Adding the mixed alkali liquor and the mixed metal liquor into a centrifugal pump according to the volume ratio of 1.3-1.5:1, carrying out high-speed collision neutralization, controlling the pH value of slurry in the neutralization process to be 7.5-8.5, the neutralization temperature to be 83 ℃, the neutralization time to be 75 minutes, and carrying out heat aging for 80 minutes at 90 ℃ after the neutralization is finished; then filtering and washing the materials by a plate-and-frame filter until Na in the materials 2 The O content is lower than 300mg/kg, then the material moisture is dried to be within 5% by a spray drying or drying box, and finally the catalyst powder is obtained by roasting for 3 hours at 450 ℃;
step 5, preparing a catalyst: 200g of catalyst powder, 20g of pure calcium aluminate cement and 3g of graphite are taken, the mixture is ball-milled in a 1L ball mill until the granularity of the mixture passes through 200 meshes, 68g of desalted water is added for rolling and granulating, the mixture is dried until the water content of the mixture is 8%, and the mixture is pressed into a phi 5X 5mm black cylinder, thus obtaining the finished catalyst particles.
Test examples
Catalyst Activity test comparison
FIG. 1 shows a device for evaluating the activity of a catalyst, wherein 30mL of catalyst particles having the original particle size (. Phi.5X15 mm particles) were first charged into the isothermal zone of the reactor, and then H used for the catalyst activation was measured in accordance with Table 1 2 -N 2 Requiring activation at 230 ℃ for 18 hours; then, the reaction mixture was changed to the raw material gas for detection shown in Table 1 and was treated with H 2 Desalted water was metered in at an O/CO volume ratio of 1.5, the internal temperature of the vaporizer was controlled at 250℃and the reactor was tested as required in Table 2.
The performance of the catalyst prepared in the above example (in which example 5 is a preparation method of a cesium-free catalyst suitable for CO wide temperature shift) was tested, the test apparatus is shown in fig. 1, the composition of feed gas is shown in table 1 below, and the test conditions are shown in table 2 below:
TABLE 1 feed gas composition v%
Table 2 test conditions
The results of the catalyst activity test are shown in fig. 2 and 3:
FIG. 2 is a graph of example catalyst initial activity;
FIG. 3 is a graph of the post heat resistance activity of the example catalyst;
the test results in FIG. 2 show that the catalysts in examples 1-5 all have a CO conversion of greater than 80% and good initial activity in the range of 200-400 ℃;
the test results in fig. 3 show that the CO conversion rate of the catalysts in examples 1 to 5 is still higher than 75% in the range of 200 to 400 ℃ after heat resistance, and the catalysts have good activity and good thermal stability after heat resistance;
table 3 comparison of methanol content in tail gas at 250 c for the catalyst of the example
As shown in Table 3, the cesium zincate auxiliary agent is added in examples 1-4, the methanol byproduct is obviously lower in the reaction process, and the cesium is not contained in example 5, the methanol byproduct is obviously higher than that in examples 1-4, and the cesium zincate addition is more beneficial to improving the effective utilization rate of CO.
Claims (8)
1. A wide temperature shift catalyst suitable for high CO is characterized by comprising CuO, znO and Al 2 O 3 ，MnO 2 ，CaO，Cs 2 O, where CuThe content of O is 25-35wt%, the content of ZnO is 25-40wt%, and Al 2 O 3 The content of (C) is 15-30wt%, mnO 2 4-8wt% of CaO, 1-3wt% of Cs 2 The content of O is 0.3-0.5wt%; the preparation method of the wide temperature shift catalyst suitable for high CO comprises the following steps:
step 1, calcining pseudo-boehmite for 4-10 hours at 850-1000 ℃ to obtain mixed crystal phase Al with good thermal stability and larger specific surface area 2 O 3 Then calcined Al 2 O 3 Grinding to above 200 mesh to obtain Al 2 O 3 Powder is reserved for standby;
step 2, cu (NO) 3 ) 2 、Zn(NO 3 ) 2 、Mn(NO 3 ) 2 Preparing a mixed solution with the total concentration of metal nitrate of 130-190g/L, and adding prepared Al 2 O 3 Powder, al 2 O 3 The ratio of the mass of the powder to the total mass of the metal salt in the mixed solution is 1.5-3: 13 to 19, and Al is added under the condition of stirring rotation speed of 300 to 450 revolutions per minute 2 O 3 Acidifying and impregnating the powder for 1-2h to form mixed slurry, emulsifying the mixed slurry for 30-60min by a three-stage emulsifying pump, and heating the slurry with uniformly dispersed phases to 80-90 ℃ under stirring to obtain mixed slurry liquid for later use;
step 3, na is carried out 2 CO 3 With NaHCO 3 The mixed alkali liquor and the mixed slurry of the mixture are subjected to high-speed collision neutralization by 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 subjected to heat aging for 60-120min at 85-100 ℃, and the materials are filtered and washed by a filter until Na in a filter cake is obtained 2 O is lower than 300mg/kg, then the washed filter cake is dried to the moisture content of less than 5% by a drying box, and finally the catalyst powder is obtained by roasting for 2-4 hours in a calciner at 400-600 ℃;
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 size is all passed through a 200-mesh sieve, rolling the ball-milled mixed material and desalted water with the mass of 25-35%, granulating, and when the water content of the granulated material is 5-10%, pressing the material into phi 5X 5mm black cylinders, thus obtaining the finished catalyst particles.
2. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: in step 1, pseudo-boehmite is calcined at 900 ℃ for 6 hours.
3. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: mixed crystal phase Al in step 1 2 O 3 The specific surface area of (2) is more than or equal to 200m 2 /g。
4. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: in step 2, cu (NO) 3 ) 2 The content of Zn (NO) is 60-80g/L 3 ) 2 The content is 60-90g/L, mn (NO) 3 ) 2 The content is 10-20g/L.
5. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: na in step 3 2 CO 3 With NaHCO 3 The mass ratio of the alkali solution to the mixed alkali solution is 2:8-8:2, and the total concentration of the mixed alkali solution is 80-120g/L.
6. A wide temperature shift catalyst for high CO according to claim 5, wherein: na in step 3 2 CO 3 With NaHCO 3 The mass ratio of (3:7) to (7:3).
7. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: na in step 3 2 CO 3 With NaHCO 3 The volume ratio of the mixed alkali liquor to the mixed slurry is 1.3-1.5:1.
8. A wide temperature shift catalyst for high CO according to claim 1, characterized in that: preparation of cesium zincate, basic zinc carbonate, cesium carbonate and desalted water are mixed according to a mole ratio of 1:2: mixing the materials in a proportion of 10 uniformly, and roasting the mixture at 400-500 ℃ for 2-4 hours to obtain cesium zincate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111000036.6A CN113600207B (en) | 2021-08-27 | 2021-08-27 | Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111000036.6A CN113600207B (en) | 2021-08-27 | 2021-08-27 | Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113600207A CN113600207A (en) | 2021-11-05 |
| CN113600207B true CN113600207B (en) | 2023-06-30 |
Family
ID=78309641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111000036.6A Active CN113600207B (en) | 2021-08-27 | 2021-08-27 | Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113600207B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115555028B (en) * | 2022-09-30 | 2023-09-05 | 四川蜀泰化工科技有限公司 | Methanol synthesis catalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK545989D0 (en) * | 1988-11-03 | 1989-11-02 | Basf Ag | COPPER CONTAINING CATALYST FOR CONVERSION AT LOW TEMPERATURES |
| JPH08173809A (en) * | 1994-12-16 | 1996-07-09 | China Petrochem Corp | Catalyst for conversion of carbon monoxide and method using the same |
| KR20080011628A (en) * | 2006-07-31 | 2008-02-05 | 한국화학연구원 | Catalyst for preparing methanol and dimethyl ether at the same time from syngas and process for preparing same |
| CN101204660A (en) * | 2006-12-20 | 2008-06-25 | 辽宁石油化工大学 | A kind of deoxidation catalyst and its preparation method and application |
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN103263929A (en) * | 2013-06-14 | 2013-08-28 | 中国科学院过程工程研究所 | Cuo/CexZr1-xO2-M high-temperature water gas conversion catalyst in IGCC (Integrated Gasification Combined Cycle) system, and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69513792T2 (en) * | 1995-01-11 | 2000-04-27 | United Catalysts Inc., Louisville | Activated and stabilized copper oxide and zinc oxide catalyst and process for its manufacture |
| RU2175265C1 (en) * | 2000-07-28 | 2001-10-27 | Открытое акционерное общество "Катализатор" | Low-temperature carbon monoxide conversion catalyst and method of preparation thereof |
| JP3837520B2 (en) * | 2002-10-07 | 2006-10-25 | 独立行政法人産業技術総合研究所 | Catalyst for CO shift reaction |
| CN101745404A (en) * | 2009-12-22 | 2010-06-23 | 上海大学 | Multi-metal composite oxide catalyst for water gas high temperature shift and preparation method thereof |
| CN112090427A (en) * | 2019-06-18 | 2020-12-18 | 南京科技职业学院 | Low steam-gas ratio carbon monoxide high-temperature shift catalyst |
| CN112206763A (en) * | 2019-07-12 | 2021-01-12 | 中石化南京化工研究院有限公司 | Copper-based low-temperature shift catalyst and preparation method thereof |
-
2021
- 2021-08-27 CN CN202111000036.6A patent/CN113600207B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK545989D0 (en) * | 1988-11-03 | 1989-11-02 | Basf Ag | COPPER CONTAINING CATALYST FOR CONVERSION AT LOW TEMPERATURES |
| JPH08173809A (en) * | 1994-12-16 | 1996-07-09 | China Petrochem Corp | Catalyst for conversion of carbon monoxide and method using the same |
| KR20080011628A (en) * | 2006-07-31 | 2008-02-05 | 한국화학연구원 | Catalyst for preparing methanol and dimethyl ether at the same time from syngas and process for preparing same |
| CN101204660A (en) * | 2006-12-20 | 2008-06-25 | 辽宁石油化工大学 | A kind of deoxidation catalyst and its preparation method and application |
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN103263929A (en) * | 2013-06-14 | 2013-08-28 | 中国科学院过程工程研究所 | Cuo/CexZr1-xO2-M high-temperature water gas conversion catalyst in IGCC (Integrated Gasification Combined Cycle) system, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Catalytic Activity of Methanol Steam Ｒeforming Cu － based Catalysts;严会成等;《山东化工》;第44卷(第15期);全文 * |
| Zn-Ni 型甲醇水蒸气高温重整制氢催化剂;严会成等;《山东化工》;第47卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113600207A (en) | 2021-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106040271B (en) | A kind of preparing propylene by dehydrogenating propane catalyst and preparation method thereof | |
| DE19653629A1 (en) | Monoclinic zirconium oxide with a high surface area | |
| CN110624599B (en) | Methanol synthesis catalyst and preparation method thereof | |
| CN113600207B (en) | Wide-temperature conversion catalyst applicable to high CO and preparation and application thereof | |
| CN112517012A (en) | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation | |
| CN110876940B (en) | Sulfur-tolerant shift catalyst and preparation method thereof | |
| CN110327907A (en) | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof | |
| CN109046379A (en) | A kind of perovskite composite oxides load platinum catalyst and its preparation and application | |
| CN106622276B (en) | methane low-temperature combustion catalyst for fluidized bed reactor and preparation method and application thereof | |
| CN113509937B (en) | Copper-containing catalyst and preparation method thereof | |
| CN105013495B (en) | Mg-Al composite oxide is methanation catalyst of carrier and preparation method thereof | |
| CN106669728A (en) | Integral-type low-temperature SCR denitration catalyst and preparation method thereof | |
| CN111318296A (en) | A kind of preparation method and application of supported cobalt/carbon nanotube material derived from zeolite imidazole framework material | |
| CN115555028B (en) | Methanol synthesis catalyst and preparation method thereof | |
| CN112237922A (en) | Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN111841555B (en) | Direct cracking of methanol to produce CO and H 2 Catalyst, preparation method and application | |
| CN101264450A (en) | Preparation method of sulfur-resistant molybdenum-based catalyst by all-microwave method | |
| CN100453178C (en) | Catalyst for synthesizing iso-propylbenzene | |
| CN111151261B (en) | Catalyst for preparing ethanol by acetate hydrogenation and application thereof | |
| CN106861730A (en) | A kind of catalyst and preparation method for C 5 petroleum resin hydrogenation | |
| CN113731422A (en) | Preparation method of slurry bed methane synthesis catalyst | |
| CN115318288A (en) | A kind of furfural liquid-phase hydrogenation to furfuryl alcohol catalyst and preparation and application | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN113908845B (en) | Energy-saving and environment-friendly method for preparing sulfur-tolerant shift catalyst | |
| CN112090427A (en) | Low steam-gas ratio carbon monoxide high-temperature shift catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |