CN1304111C - Copper-manganese base high temperature transformation catalyst and preparation method thereof - Google Patents
Copper-manganese base high temperature transformation catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a copper-manganese based high-temperature conversion catalyst and a preparation method thereof. The general formula of the copper-manganese based high-temperature conversion catalyst is Cua(Mn)bO4-M, wherein a is from 1.0 to 1.5, and b is from 1.5 to 2.0; the active constituent is Cua(Mn)bO4, and M is a thermostable auxiliary agent; the active constituent Cua(Mn)bO4 accounts for 95 wt% to 98 wt%, and the thermostable auxiliary agent M accounts for 2 wt% to 5 wt%. The preparation method comprises the steps of preparing copper-manganese water solution, preparing catalyst precursors, preparing the mixture of copper-manganese precipitates, preparing copper-manganese based catalysts, etc. The preparation method has simple technology and low cost; the prepared catalyst has good heat resistance and high low-temperature activity.
Description
Technical Field
The invention relates to a high-temperature shift catalyst, in particular to a copper-manganese based high-temperature shift catalyst and a preparation method thereof.
Background
The CO shift reaction plays an important role in hydrogen production and refining and purifying synthesis gas, and since 1921 the reaction is industrially applied, the iron-chromium-based high-temperature shift catalyst plays an important role. The catalyst has the advantages of wide active temperature, good thermal stability, strong antitoxic performance and the like, and the basic composition of the catalyst is rarely changed for many years. However, in addition to the environmental pollution, the main technical problem in the use of the iron-chromium-based catalyst is that a large amount of excessive water vapor is required to prevent the active component(Fe) in the catalyst3O4) The catalyst is excessively reduced, so that the activity of the catalyst is reduced, and more seriously, a series of side reactions such as Fischer-Tropsch (Fischer-Tropsch) reaction and the like occur, so that the requirements of a novel energy-saving process cannot be met. Even the capability of the improved iron-chromium high-temperature shift catalyst for resisting Fischer-Tropsch side reaction still has a certain limit, namely the capability of the improved iron-chromium high-temperature shift catalyst for resisting Fischer-Tropsch side reaction2O/CO) still produces significant amounts of F-T side reaction products at lower conditions, with serious consequences such as reduced hydrogen production, poisoning of the lean catalyst, deterioration of operating conditions, etc., and therefore the underlying approach to eliminating the Fischer-tropsch side reaction is to develop a non-iron containing catalyst.
The first reported studies on non-iron-based high temperature shift catalysts to overcome the Fischer-Tropsh side reaction of iron-based high temperature shift catalysts were the Cu-based shift catalysts LK-811 and KK142 reported by Topsol, Denmark, which have a maximum heat resistance temperature of about 350-390 ℃ and are much higher than the heat resistance temperature (250 ℃) of Cu-Zn low temperature shift catalysts, but have a certain difference in heat resistance compared with the heat resistance temperature (480-500 ℃) of iron-based high temperature shift catalysts. The copper-manganese high-temperature-change catalyst prepared by hydrothermal synthesis reaction is reported almost simultaneously in Japan and south Africa, but the maximum heat-resisting temperature of the two catalysts is below 400 ℃.
The above reports almost all adopt the harsh preparation process conditions (the temperature for catalyst neutralization and precipitation is about 150 ℃).
Disclosure of Invention
The invention aims to provide a copper-manganese based high-temperature shift catalyst.
The general formula of the copper-manganese based high-temperature shift catalyst provided by the invention is as follows: cua(Mn)bO4M, wherein a is 1.0 to 1.5, b is 1.5 to 2.0, and the active ingredient is Cua(Mn)bO4M is a heat stabilizing additive; the active component Cua(Mn)bO4The content of (A) is 95-98% by weight and the content of the heat stabilizing auxiliary M is 2-5% by weight.
The thermal stabilizing additive M is selected from CeO2Or Al2O3One or two of them; the catalyst Cua(Mn)bO4-M has a single inverted spinel structure.
Another object of the present invention is to provide a method for preparing the above catalyst, which comprises the steps of:
(a) preparing copper and manganese aqueous solution
Taking soluble salts of copper and manganese according to the proportion of 1: 1-1: 3 of the dosage ratio of copper and manganese in terms of mol, mixing and dissolving the soluble salts in water to ensure that the concentration of the solution is 0.1-0.5M, stirring and heating to 40-60 ℃ at the stirring speed of 240 revolutions per minute, and keeping the temperature for 0.5-1.0 hour at constant temperature to ensure that the soluble salts are completely dissolved and fully mixed;
(b) precursor for preparing copper-manganese based catalyst
Gradually adding an alkaline solution into the prepared aqueous solution, adjusting the pH value of the solution to9-10, gradually adding a thermal stabilizing auxiliary agent with the amount of 2.5-5.5% by weight of the finished product in the neutralization process, and thermally boiling the obtained solution at the temperature of 60-75 ℃ for 30-60 minutes under normal pressure to obtain a catalyst precursor with a layered hydrated crystal as a main structure;
(c) preparation of copper and manganese precipitate mixture
Washing the hydrated crystals obtained after the hot boiling with water to remove SO4 2-、NO3 -And CO3 2-Separating solid from liquid by centrifugal filtration to obtain solid copper-manganese precipitate mixture, and removing physically bound water from the copper-manganese precipitate mixture by heating;
(d) preparation of copper-manganese-based catalyst
Roasting the copper and manganese precipitate mixture without the physically bound water at the temperature of 500-650 ℃ under normal pressure for 3-5 hours, wherein the temperature rise rate during roasting is controlled at 3-5 ℃/min, and the crystal phase of the obtained product is Cua(Mn)bO4-M of a copper manganese based catalyst.
The copper soluble salt is selected from one of copper sulfate and copper nitrate; the manganese soluble salt is selected from one of manganese sulfate and manganese nitrate; the thermal stabilizing additive in step (b) is selected from CeO2Or Al2O3One or two of the thermal stabilizing auxiliary agents, the particle size of the thermal stabilizing auxiliary agent is 60-140 meshes; the alkaline solution is selected from NaOH, KOH, Na2CO3、K2CO3One of (1); the precursor of the catalyst has the general formula: [ Cu]6-xMnx(OH)12]x+[(An-)x/n·yH2O]x-Wherein x is more than or equal to 0.9 and less than or equal to 4.2, An-Is an anion.
The catalyst of the invention does not contain iron, thereby eliminating Fischer-Tropsch side reaction, and obviously improving heat resistance and low-temperature activity compared with the prior similar catalyst; the preparation method of the invention adopts the conventional precipitation method, controls the form of the catalyst precursor by controlling the p H value of the solution and the dropping amount of the alkaline solution in the neutralization process, thereby obtaining the final structure of the catalyst, and has simple process and low cost.
Drawings
The attached figure is a process flow diagram for preparing the catalyst of the invention.
Detailed Description
The following detailed description is merely illustrative of the invention and is not to be construed as limiting the invention.
EXAMPLE 1 preparation of 40 g of a copper manganese-based catalyst
(a) Preparation of aqueous copper and manganese solutions
Weighing CuSO4·5H2O45.1 g, MnSO4·H261.1 g of O, the mixture was mixed and placed in a 2000ml beaker to prepare 1200ml of a mixed solution, the mixed solution was placed on an electric furnace and heated to 45 ℃ with stirring, the stirring rate was maintained at about 240 rpm, and then the temperature was maintained for 30 minutes to allow the mixture to be sufficiently mixed and dissolved.
(b) Preparation of copper-manganese-based catalyst precursor
NaOH 48 g was weighed to prepare a solution 300ml, which was then transferred to a ball funnel. Weighing Al2O30.8 g of CeO20.8 g, adding Al in a mortar2O3、CeO2Grinding the solid particles into powder with the particle size of 60-80 meshes; dropping NaOH solution into the copper-manganese aqueous solution at a rate of about 10 ml/min, observing pH change while dropping, and simultaneously adding grinded Al2O3、CeO2Powder, stopping dripping when the pH value is constant at 9.5, and then boiling for 30 minutes at 65 ℃; standing, removing supernatant after the precipitate is completely precipitated, obtaining the precipitate as a precursor of the copper-manganese catalyst, and obtaining the precursor by powder XRD and diffraction calculation in a selected area of a Transmission Electron Microscope (TEM)The chemical formula of the body is [ Cu]6-xMnx(OH)12]x+[(An-)x/n·yH2O]x-Wherein x is more than or equal to 0.9 and less than or equal to 4.2, An-Is SO4 2-The structure is a layered hydrated crystal.
(c) Preparation of copper-manganese-based catalyst mixture
Putting the precursor of the copper-manganese-based catalyst into a 5000ml beaker, repeatedly washing the precursor by using tap water, and removing SO4 2Impurities, stirring the solution at the initial stage of washing, and dripping 10% BaCl into the supernatant2When no white precipitate is observed in the solution, the solution can be considered to be washed thoroughly; and filtering the precipitate to separate solid from liquid, putting the obtained filter cake into a beaker, putting the mixture into an oven, and drying for 4 hours at 120 ℃, wherein the heating rate of the oven is controlled at 3 ℃/min, so as to obtain the copper-manganese precipitate mixture without physically bound water.
(d) Preparation of copper-manganese-based catalyst
Grinding the dried substance, putting the ground substance into a muffle furnace, roasting the ground substance for 4 hours at the temperature of 550 ℃, controlling the temperature rise rate of the muffle furnace at 5 ℃/min, and obtaining the roasted substance, namely the copper-manganese-based high-temperature conversion catalyst: cu1.46Mn1.54O4-(Al2O3+CeO2)。
The Cu can be determined by powder XRD and diffraction calculation of selected area of Transmission Electron Microscope (TEM)1.46Mn1.54O4-(Al2O3+CeO2) And has a single inverted spinel structure.
Solution reaction during neutralization:
decomposition reaction in the drying process and combination reaction in the roasting process:
wherein x is more than or equal to 0.9 and less than or equal to 4.2.
Example 2 preparation of 10 g of a copper manganese-based catalyst
(a) Preparation of aqueous copper-manganese solutions
Weighing Cu (NO)3)·3H2O10.0 g, MnSO4·H215.3 g of O, and the mixture was mixed and placed in a 2000ml beaker to prepare 500ml of a mixed solution, and the mixed solution was placed on an electric furnace and heated to 45 ℃ with stirring, and the stirring rate was maintained at about 240 rpm, and then the temperature was maintained for 30 minutes to sufficiently dissolve the mixed solution.
(b) Preparation of copper-manganese-based catalyst precursor
15 g of KOH was weighed out to prepare 75ml of a solution, which was then transferred to a ball funnel. Weighing CeO20.3 g of CeO in a mortar2Grinding the solid particles into powder with the particle size of 80-100 meshes; dropping NaOH solution into the copper-manganese aqueous solution at a rate of about 8 ml/min, observing pH change while dropping, and simultaneously adding grinded CeO2Powder, stopping dripping when the pH value is constant at 10, and then boiling for 30 minutes at the temperature of 60 ℃; standing, and removing supernatant liquor after complete precipitation, wherein the obtained precipitate is a precursor of the copper-manganese catalyst; the chemical structure of the precursor is [ Cu]obtained by the calculation of powder XRD and the diffraction of a selected area of a Transmission Electron Microscope (TEM)6-xMnx(OH)12]x+[(An-)x/n·yH2O]x-Wherein A isn-Is NO3 -、SO4 2-X is more than or equal to 0.9 and less than or equal to 4.2, and the structure is a layered hydrated crystal.
(c) Preparation of copper-manganese-based catalyst mixture
Putting the precursor of the copper-manganese-based catalyst into a 5000ml beaker, repeatedly washing with tap water to remove NO3 -、SO4 2+Impurities, stirring the solution at the initial stage of washing, and dripping 10% BaCl into the supernatant2When no white precipitate is observed in the solution, the solution can be considered to be washed thoroughly; and filtering the precipitate to separate solid from liquid, putting the obtained filter cake into a beaker, putting the mixture into an oven, and drying for 4 hours at 120 ℃, wherein the heating rate of the oven is controlled at 3 ℃/min, so as to obtain the copper-manganese precipitate mixture without physically bound water.
(d) Preparation of copper-manganese-based catalyst
And grinding the dried substance, putting the ground substance into a muffle furnace, and roasting the ground substance for 5 hours at 550 ℃, wherein the heating rate of the muffle furnace is controlled at 5 ℃/min. The calcined substance is the required catalyst: cu1.36Mn1.64O4-CeO2。
The Cu can be determined by powder XRD and diffraction calculation of selected area of Transmission Electron Microscope (TEM)1.36Mn1.64O4-CeO2And has a single inverted spinel structure.
Solution reaction during neutralization:
decomposition reaction in the drying process and combination reaction in the roasting process:
wherein x is more than or equal to 0.9 and less than or equal to 4.2, An-Is NO3 -、SO4 2-。
Example 3 preparation of 100 grams of a copper manganese based high temperature shift catalyst
(a) Preparation of aqueous copper-manganese solutions
Weighing CuSO4·5H2O110 g, Mn (NO)3)2·6H2And O300 g, mixing and putting the mixture intoa 3000ml beaker to prepare 1200ml of mixed solution, putting the mixed solution on an electric furnace, heating the mixed solution to 45 ℃ while stirring, keeping the stirring speed at about 240 revolutions per minute, and keeping the constant temperature for 30 minutes to fully dissolve the mixed solution.
(b) Preparation of copper-manganese-based catalyst precursor
110 g of NaOH was weighed out to prepare 800ml of a solution, which was then transferred to a ball funnel. Weighing Al2O34.8 g, mixing Al in a mortar2O3Grinding the solid particles into powder with the particle size of 80-100 meshes; dropping NaOH solution into the mixed solution of copper and manganese aqueous solution at the rate of about 30 ml/min, observing pH value change while dropping, and simultaneously adding ground Al2O3Powder, stopping dripping when the pH value is constant at 9, and then boiling for 30 minutes at 70 ℃; standing, and removing supernatant liquor after complete precipitation, wherein the obtained precipitate is a precursor of the copper-manganese catalyst; the chemical general formula of the precursor is [ Cu]obtained by calculation of powder XRD and selective diffraction of a Transmission Electron Microscope (TEM)6-xMnx(OH)12]x+[(An-)x/n·yH2O]x-Wherein x is more than or equal to 0.9 and less than or equal to 4.2, the structure is a layered hydrated crystal, An-Is NO3 -、SO4 2-。
(c) Preparation of copper-manganese-based catalyst mixture
Putting the precursor of the copper-manganese-based catalyst into a 5000ml beaker, repeatedly washing with tap water to remove NO3 2-、SO4 2-Impurities, stirring the solution at the initial stage of washing, and dripping 10% BaCl into the supernatant2When no white precipitate is observed in the solution, the solution can be considered to be washed thoroughly; and filtering the precipitate to separate solid from liquid, putting the obtained filter cake into a beaker, putting the mixture into an oven, and drying for 4 hours at 120 ℃, wherein the heating rate of the oven is controlled at 3 ℃/min to obtain the copper-manganese precipitate mixture with the water phase removed.
(d) Preparation of copper-manganese-based catalyst
Grinding the dried substance, putting the ground substance into a muffle furnace, roasting the ground substance for 3 hours at the temperature of 600 ℃, controlling the temperature rise rate of the muffle furnace at 5 ℃/min, and obtaining the roasted substance as the required catalyst: cu1.42Mn1.58O4-Al2O3。
The Cu can be determined by powder XRD and diffraction calculation of selected area of Transmission Electron Microscope (TEM)1.42Mn1.58O4-Al2O3And has a single inverted spinel structure.
Solution reaction during neutralization:
decomposition reaction in the drying process and combination reaction in the roasting process:
wherein x is more than or equal to 0.9 and less than or equal to 4.2, An-Is NO3 -、SO4 2-。
Activity test experiment
The activity of the copper-manganese-based high-temperature shift catalyst prepared by the method is obviously improved compared with that of the high-temperature shift catalyst in the prior art, and according to the test method and the standard of national standard ZBG74001-89, the activity data of the copper-manganese-based high-temperature shift catalyst disclosed by the invention is compared with that of a domestic high-quality high-temperature shift catalyst B113-2 (provided by Liaohe catalyst Co., Ltd., southern China, Panjin) and an iron-based high-temperature shift catalyst C12-4 (provided by United Catalysts Inc. in the United states) as follows (CO conversion rate at 350 ℃):
keeping the temperature of 530 ℃ for 15 hours in a reaction atmosphere
The data in the table illustrate: after the catalyst is subjected to heat resistance at 530 ℃ for 15 hours, the activity at 350 ℃ is obviously higher than that of B113-2 and higher than that of C12-4, and the activity at 250 ℃ and 300 ℃ of the catalyst is much higher than that of B113-2 and C12-4, so that the heat resistance of the catalyst is good, and the low-temperature activity of the catalyst is obviously higher than that of B113-2 and C12-4.
In conclusion, the activity of the high-temperature shift catalyst of the invention is obviously improved compared with the prior iron-based high-temperature shift catalyst, so that the high-temperature shift catalyst can be used as a substitute of the iron-based high-temperature shift catalyst, thereby eliminating a series of serious consequences such as reduction of hydrogen yield, poisoning of the low-temperature shift catalyst, deterioration of the operation state and the like caused by Fischer-Tropsch (Fischer-Tropsch) side reaction.
Claims (8)
1. The copper-manganese based high-temperature shift catalyst has a general formula: cua(Mn)bO4M, wherein a is 1.0 to 1.5, b is 1.5 to 2.0, and the active ingredient is Cua(Mn)bO4M is a heat stabilizing additive;the thermal stabilizing additive M is selected from CeO2Or Al2O3One or two of them; the active component Cua(Mn)bO4The content of (A) is 95-98% by weight and the content of the heat stabilizing auxiliary M is 2-5% by weight.
2. The catalyst of claim 1, characterized in that Cua(Mn)bO4-M has a single inverted spinel structure.
3. A method for preparing the catalyst of claim 1, comprising the steps of:
(a) preparing copper-manganese aqueous solution
Taking soluble salts of copper and manganese according to the proportion that the dosage ratio of copper and manganese is 1: 1-1: 3 in terms of mol, mixing and dissolving the soluble salts in water to ensure that the concentration of the solution is 0.1-0.5mol/l, stirring and heating to 40-60 ℃ at the stirring speed of 240 revolutions per minute, and keeping the temperature for 0.5-1.0 hour at constant temperature to ensure that the soluble salts are completely dissolved and fully mixed;
(b) precursor for preparing copper-manganese based high-temperature shift catalyst
Gradually adding an alkaline solution into the prepared aqueous solution, adjusting the pH value of the solution to 9-10, gradually adding a thermal stabilizing auxiliary agent accounting for 2.5-5.5% of the weight of a finished product in the neutralization process, and thermally boiling the obtained solution at the temperature of 60-75 ℃ for 30-60 minutes under normal pressure to obtain a catalyst precursor with a layered hydrated crystal as a main structure;
(c) preparation of copper-manganese precipitation mixture
Washing the hydrated crystals obtained after the hot boiling with water to remove SO4 2-、NO3 -And CO3 2-Separating solid from liquid by adopting a centrifugal filtration method to obtain solid which is a copper-manganese precipitate mixture, and heating to remove physically bound water in the copper-manganese precipitate mixture;
(d) preparation of copper-manganese-based catalyst
Roasting the copper-manganese precipitate mixture without physically bound water at the temperature of 500-650 ℃ under normal pressure for 3-5 hours, wherein the temperature rise rate during the roasting is controlled to be 3The temperature is between 5 ℃ below zero and minute, and the prepared crystal phase is Cua(Mn)bO4-M of a copper manganese based high temperature shift catalyst.
4. The method for preparing a catalyst according to claim 3, wherein the copper-soluble salt is selected from one of copper sulfate and copper nitrate.
5. The method for preparing a catalyst according to claim 3, characterized in that the manganese-soluble salt is selected from one of manganese sulfate and manganese nitrate.
6. The catalyst preparation process according to claim 3, wherein the particle size of the thermal stabilizing aid in the step (b) is 60 to 140 mesh.
7. The method for preparing catalyst according to claim 3, wherein the alkaline solution in step (b) is selected from NaOH, KOH, Na2CO3、K2CO3One kind of (1).
8. The method of preparing a catalyst according to claim 3, wherein the precursor of the catalyst in the step (b) has a general formula of: [ Cu]6-xMnx(OH)12]x+[(An-)x/n·yH2O]x-Wherein x is more than or equal to 0.9 and less than or equal to 4.2, An-Is an anion.
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| US8828903B2 (en) * | 2008-11-10 | 2014-09-09 | Basf Corporation | Copper catalyst for dehydrogenation application |
| CN103861611A (en) * | 2014-03-17 | 2014-06-18 | 北京工业大学 | Preparation method and application of Cu-Mn catalyst loaded on aluminum-pillared montmorillonite |
| CN111617769B (en) * | 2020-07-02 | 2023-05-23 | 四川亚联氢能科技股份有限公司 | Preparation method of chromium-free wide-temperature water-gas shift catalyst, catalyst and application |
| CN114570383B (en) * | 2022-03-30 | 2023-06-23 | 西安交通大学 | A kind of copper-manganese composite catalyst and its preparation method and application |
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| JPS6377546A (en) * | 1986-09-17 | 1988-04-07 | Nissan Gaadoraa Shokubai Kk | Catalyst for conversion of carbon monoxide and its production |
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| JPS6377546A (en) * | 1986-09-17 | 1988-04-07 | Nissan Gaadoraa Shokubai Kk | Catalyst for conversion of carbon monoxide and its production |
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