CN110227449B - High-temperature-resistant catalyst, and preparation method and application thereof - Google Patents
High-temperature-resistant catalyst, and preparation method and application thereof Download PDFInfo
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- CN110227449B CN110227449B CN201910519404.4A CN201910519404A CN110227449B CN 110227449 B CN110227449 B CN 110227449B CN 201910519404 A CN201910519404 A CN 201910519404A CN 110227449 B CN110227449 B CN 110227449B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
Abstract
The invention provides a high-temperature-resistant catalyst, a preparation method and application thereof. The additive is used as a coal water slurry additive, so that the slurry forming performance of the coal water slurry is more stable, the framework and the active components of the catalyst are effectively protected at high temperature and high pressure, the high yield of formic acid is achieved, the concentration of calcium and magnesium ions in the grey water can be regulated and controlled by generating the required formic acid according to the adding amount of the catalyst, and the scaling phenomenon is prevented.
Description
Technical Field
The invention relates to a high-temperature-resistant catalyst, a preparation method and application thereof, in particular to a coal water slurry additive applied to a grey water descaling system.
Technical Field
The ash water produced by the coal gasification device contains high-content calcium, magnesium and other ions, and CaCO can be generated along with the rise of pH value3、Mg(OH)2And the like, which is basically not influenced by the flocculating agent, can be suspended in the grey water in the form of molecular groups and finally sequentially precipitated into various storage tanks and pipelines of the grey water, so that scaling is caused at positions of gasification furnaces, washing tower internals, chilling water pipelines and the like, and the severe scaling can cause frequent shutdown and scale removal of the device and influence the stable operation of equipment.
In order to ensure that the alkalinity and the hardness of the grey water reachIt is desirable to reduce the occurrence of fouling by attempting to adjust the pH by adding hydrochloric acid to the grey water, but this increases the Cl in the grey water-The concentration and the ash water are easy to cause the corrosion of the equipment pipeline in the recycling process.
Patent CN106673292 discloses a pretreatment method of gasified ash water, which comprises, before generating ash water in a gasification section, carrying out pretreatment by steps of alkali stripping, mixing flash evaporation, acid addition, partial neutralization, acid inhibition, etc., to reduce the content of calcium and magnesium ions in the ash water, and the process is complicated and not beneficial to operation.
Patent CN207391109 discloses a gasified ash water pretreatment system with a forced descaling device, which comprises an ash water reactor and a settler, wherein the ash water reactor and the settler are provided with the forced descaling device, and the equipment investment cost is high.
The above patents consider descaling from the aspects of increasing equipment and improving flow of the grey water system, and have high process investment, high energy consumption and complex operation.
Formic acid, a commonly used scale remover, is also used for grey water scale removal, however, grey water scale removal involves a plurality of equipment pipelines in the system, and the scale removal effect is greatly reduced due to different addition positions, addition amounts and mixing effects after addition of the formic acid.
The synthesis gas in the gasifier contains CO2、H2And the formic acid can be generated under the catalytic action of the catalyst, however, the framework and the active components of the common formic acid catalyst can be sintered, collapsed and inactivated in the gasification furnace due to the overhigh temperature in the gasification furnace, and the catalytic action cannot be realized.
Disclosure of Invention
Aiming at the problems, the invention provides a high-temperature-resistant catalyst, a preparation method and application thereof, wherein the catalyst can be directly used as a coal water slurry additive to be added into coal water slurry, so that the slurry forming property of the coal water slurry is more stable, part of synthesis gas can be converted into formic acid, and the ash water scale generated by a gasification furnace can be prevented.
The invention provides a high-temperature-resistant catalyst which comprises an active component, an auxiliary agent and a carrier, wherein the active component is ruthenium, the auxiliary agent is titanium, and the carrier is alumina or silica pretreated by coal water slurry.
The ruthenium is selected from one or more of ruthenium trichloride, ruthenium acetate, ruthenium acetylacetonate and ruthenium dodecacarbonyl, preferably ruthenium chloride or ruthenium acetate;
the titanium is selected from one or more of titanium tetrachloride, titanium trichloride, titanocene dichloride and tetrabutyl titanate, and the titanium trichloride or titanocene dichloride is preferred.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) preparing an impregnation solution, wherein the solution contains: an active component precursor, an auxiliary agent precursor, citric acid and glycol;
preferably, the concentration of the active component precursor is 0.5-2 g/100mL based on ruthenium, the concentration of the auxiliary agent precursor is 0.05-0.2 g/100mL based on titanium, the concentration of citric acid is 0.3-2.8 g/100mL, and the concentration of ethylene glycol is 0.5-3.4 g/100 mL;
(2) uniformly mixing the pre-carrier and the water-coal-slurry solution, transferring the mixture into a high-pressure reaction kettle, keeping the pressure at 2-4 MPa (absolute pressure) in a reducing atmosphere at the temperature of 500-800 ℃, and reacting for 3-5 hours;
(3) filtering the reaction mixture obtained in the step (2), drying the obtained solid sample, and roasting at 600-1000 ℃ for 2-4 h to obtain a carrier;
(4) and (3) impregnating the carrier obtained in the step (3) with the impregnation solution obtained in the step (1), drying, and roasting in a reducing atmosphere II to obtain the catalyst.
In the invention, the active component precursor in the step (1) is one or more of ruthenium trichloride, ruthenium acetate, ruthenium acetylacetonate and ruthenium dodecacarbonyl, preferably ruthenium trichloride or ruthenium acetate; the auxiliary agent precursor is one or more of titanium tetrachloride, titanium trichloride, titanocene dichloride and tetrabutyl titanate, and the titanium trichloride or titanocene dichloride is preferred.
In the present invention, the preparation method of the impregnation liquid in the step (1) comprises: 1.1) dripping an active component precursor and an auxiliary agent precursor in an aqueous solution in sequence, and heating to 40-80 ℃; 1.2) sequentially adding citric acid and ethylene glycol, and carrying out constant-temperature reflux stirring for 1-2 h;
in the invention, in the step 1.1), the dropping speed of the active component precursor is 0.5-2mL/min, the dropping speed of the auxiliary agent precursor is 0.1-0.6mL/min, and the constant-temperature stirring speed is 100-300 rpm;
in the invention, the pre-carrier in the step (2) is any one of alumina or silicon oxide; the concentration of the coal water slurry is 58-68%, preferably 60-65%, and the viscosity of the coal water slurry is 700-1400 mPa & s, preferably 850-1200 mPa & s; the mass ratio of the pre-carrier to the coal water slurry is 1: 1-5: 1;
in the invention, the reducing atmosphere I in the step (2) is a mixed gas of carbon monoxide and nitrogen or a mixed gas of hydrogen and nitrogen, and the volume percentage of nitrogen in the mixed gas is 5-90%, preferably 40-70%;
in the invention, the impregnation process in the step (4) adopts equal-volume impregnation, the impregnation time is 6-10 h, the drying temperature in the step (4) is 80-180 ℃, the drying time is 4-8 h, the roasting temperature is 800-1300 ℃, and the roasting time is 1-2 h;
in the invention, the second reducing atmosphere in the step (4) is a mixed gas of hydrogen and carbon monoxide, and the volume percentage of hydrogen in the mixed gas is 30-50%.
The catalyst of the invention can be used as a coal water slurry additive to be applied to a gasification furnace to catalyze synthesis gas to generate formic acid for ash water descaling.
In the invention, the addition amount of the catalyst is different according to the concentration of calcium and magnesium ions in the grey water, and the addition amount of the catalyst is 0.01-2% of the total mass of the coal water slurry under general conditions.
The catalyst of the invention can keep better catalytic activity under the high temperature condition of the gasification furnace, catalyze the synthesis gas to generate formic acid, control the generation amount of the formic acid by controlling the dosage of the catalyst, regulate the concentration of calcium and magnesium ions in the grey water and prevent scaling phenomenon. The preparation method of the invention introduces the coal water slurry in the carrier pretreatment process, on one hand, the slurry forming performance of the coal water slurry is more stable, on the other hand, the framework and the active components of the catalyst are effectively protected at high temperature and high pressure, higher yield of formic acid is achieved, and the concentration of calcium and magnesium ions in the grey water can be regulated and controlled by generating the required formic acid according to the adding amount of the catalyst, thereby preventing scaling phenomenon.
Detailed Description
The present invention will be further described with reference to the following examples, wherein the percentages are by weight unless otherwise specified.
Example 1
200mL of ultrapure water is weighed into a three-neck flask, the stirring speed is set to be 200rpm, 14g of ruthenium trichloride solution (30 percent, alatin) is added into the flask at the speed of 1mL/min, then 3.2g of titanium trichloride solution (20 percent, alatin) is added into the flask at the speed of 0.3mL/min, after the temperature is raised to 50 ℃, 1g of citric acid (AR, national medicine) and 1.5g of ethylene glycol (AR, national medicine) are added, and the impregnation liquid L1 is obtained after constant-temperature reflux stirring for 2 hours.
Uniformly mixing alumina and a coal water slurry solution (the concentration is 62 percent and the viscosity is 1000 mPas) according to a certain proportion, transferring the mixture into a high-pressure reaction kettle, filling a mixed gas of hydrogen and nitrogen (the volume percentage of the hydrogen is 40 percent) in the kettle to 2.5MPa, heating the mixture to 700 ℃, reacting for 4 hours, filtering the reaction mixture, drying the obtained solid sample, and roasting for 4 hours at the temperature of 800 ℃ to obtain the carrier. In this example, five carriers were prepared, the mass ratios of alumina to the coal-water slurry solution were adjusted to 1:1, 2:1, 3:1, 4:1, and 5:1, respectively, and the obtained carriers were Z1, Z2, Z3, Z4, and Z5, respectively.
The carriers Z1, Z2, Z3, Z4 and Z5 are respectively impregnated by an impregnating solution L1 in an equal volume for 8 hours, then dried at 120 ℃ for 6 hours, and then heated to 1200 ℃ in an atmosphere of a mixed gas of hydrogen and carbon monoxide (the volume percentage of the hydrogen is 35%) and roasted for 1 hour to obtain the catalysts C1, C2, C3, C4 and C5.
Example 2
200mL of ultrapure water is weighed into a three-neck flask, the stirring speed is set to be 200rpm, 10g of ruthenium trichloride solution (30 percent, alatin) is added into the flask at the speed of 1mL/min, then 2.4g of titanium trichloride solution (20 percent, alatin) is added into the flask at the speed of 0.3mL/min, after the temperature is raised to 50 ℃, 1g of citric acid (AR, national medicine) and 1.5g of ethylene glycol (AR, national medicine) are added, and the impregnation liquid L2 is obtained after constant-temperature reflux stirring for 2 hours.
Uniformly mixing silicon oxide and a water-coal-slurry solution (the concentration is 62 percent and the viscosity is 1000mPa & s) in a mass ratio of 2:1, transferring the mixture into a high-pressure reaction kettle, filling a mixed gas of hydrogen and nitrogen (the volume percentage of the hydrogen is 40 percent) in the kettle to 2.5MPa, heating the mixture to 700 ℃, reacting for 4 hours, filtering the reaction mixture, drying the obtained solid sample, and roasting for 4 hours at the temperature of 800 ℃ to obtain a carrier Z6.
The carrier Z6 is respectively impregnated by impregnation liquid L2 in an equal volume for 8h, then dried for 6h at 120 ℃, and then heated to 1200 ℃ in the atmosphere of mixed gas of hydrogen and carbon monoxide (the volume percentage of the hydrogen is 35 percent) and roasted for 1h to obtain the catalyst C6.
Example 3
Uniformly mixing alumina and a water-coal-slurry solution (the concentration is 65%, and the viscosity is 1100mPa & s) in a mass ratio of 2:1, transferring the mixture into a high-pressure reaction kettle, filling a mixed gas of hydrogen and nitrogen (the volume percentage of the hydrogen is 40%) in the kettle to 2.5MPa, heating to 700 ℃, reacting for 4 hours, filtering the reaction mixture, drying the obtained solid sample, and roasting for 4 hours at 800 ℃ to obtain a carrier Z7.
The carrier Z7 is soaked in the impregnation liquid L1 for 8 hours in an equal volume mode, then is dried for 6 hours at the temperature of 120 ℃, and then is heated to 1200 ℃ in the atmosphere of mixed gas of hydrogen and carbon monoxide (the volume percentage of the hydrogen is 35 percent) and is roasted for 1 hour to obtain the catalyst C7.
Comparative example 1
This comparative example describes a process for preparing a catalyst without a support doped with a water-coal-slurry solution. Transferring the alumina into a high-pressure reaction kettle, filling mixed gas (the volume percentage of hydrogen is 40%) of hydrogen and nitrogen into the kettle to 2.5MPa, heating to 700 ℃, reacting for 4h, drying the reaction mixture, and roasting for 4h at 800 ℃ to obtain a carrier W1.
The carrier W1 was impregnated with the impregnation liquid L1 prepared in example 1 in the same volume, and then dried at 120 ℃ for 6 hours, and then calcined at 1200 ℃ for 1 hour under an atmosphere of a mixed gas of hydrogen and carbon monoxide (the volume percentage of hydrogen is 35%) to obtain a catalyst D1.
Comparative example 2
This comparative example describes a method for preparing a catalyst with a support having a high coal-water slurry ratio. Uniformly mixing alumina and a water-coal-slurry solution (the concentration is 62 percent and the viscosity is 800 mPas) in a mass ratio of 1:5, transferring the mixture into a high-pressure reaction kettle, filling mixed gas of hydrogen and nitrogen (the volume percentage of the hydrogen is 40 percent) in the kettle to 2.5MPa, heating the mixture to 700 ℃, reacting for 4 hours, filtering the reaction mixture, drying the obtained solid sample, and roasting for 4 hours at the temperature of 800 ℃ to obtain a carrier W2.
The carrier W2 was impregnated with the impregnation liquid L1 prepared in example 1 in the same volume, and then dried at 120 ℃ for 6 hours, and then calcined at 1200 ℃ for 1 hour under an atmosphere of a mixed gas of hydrogen and carbon monoxide (the volume percentage of hydrogen is 35%) to obtain a catalyst D2.
Comparative example 3
This comparative example describes a method for preparing a catalyst with a support having a high coal slurry concentration. Uniformly mixing alumina and a coal water slurry solution (the concentration is 72 percent and the viscosity is 1800mPa & s) according to the mass ratio of 2:1, transferring the mixture into a high-pressure reaction kettle, filling mixed gas of hydrogen and nitrogen (the volume percentage of the hydrogen is 40 percent) in the kettle to 2.5MPa, heating the mixture to 700 ℃, reacting for 4 hours, filtering the reaction mixture, drying the obtained solid sample, and roasting for 4 hours at the temperature of 800 ℃ to obtain a carrier W3.
The carrier W3 was impregnated with the impregnation liquid L1 prepared in example 1 in the same volume, and then dried at 120 ℃ for 6 hours, and then calcined at 1200 ℃ for 1 hour under an atmosphere of a mixed gas of hydrogen and carbon monoxide (the volume percentage of hydrogen is 35%) to obtain a catalyst D3.
Test example 1
The test example is a test for evaluating the influence of the catalyst on the slurry forming performance of the coal water slurry. Weighing 72g of coal powder, mixing with 0.2g of prepared catalysts C1, C2, C3, C4, C5, C6, C7, D1, D2 and D3 respectively, adding water to dilute to 100g, and uniformly stirring to obtain flowable coal water slurry S1, S2, S3, S4, S5, S6, S7, S8, S9 and S10.
The fluidity is detected according to the GB-/T18855-2008 standard method, the apparent viscosity of the slurry at 25 ℃ is measured by a viscometer, and the concentration of the coal slurry is measured by a rapid moisture meter, which is shown in Table 1.
Test example 2
This test example is a catalyst activity evaluation test. The catalyst activity evaluation test is carried out in an entrained flow bed reaction kettle, the reaction temperature is 1200 ℃, the reaction pressure is 6MPa, oxygen and coal water slurry are mixed and injected into a reactor, the oxygen-coal ratio is 500, and the airspeed is 2000h-1The reaction solution was analyzed for formic acid content, and the results are shown in Table 1.
Table 1 evaluation results of slurry forming performance and activity of the prepared coal water slurry.
Wherein, the fluidity of the coal water slurry is A > B > C.
From the above table, the catalyst obtained by pretreating the carrier by the method of the invention is applied to a gasification furnace as a coal water slurry additive, on one hand, the slurry forming performance of the coal water slurry can be more stable, the good fluidity can be maintained, and no unrecoverable hard precipitate can be generated after standing for 24h, on the other hand, the framework and the active components of the catalyst can be effectively protected at high temperature and high pressure, the high yield of formic acid can be achieved, and the required formic acid can be generated according to the adding amount of the catalyst to regulate the concentration of calcium and magnesium ions in the grey water, so that the scaling phenomenon can be prevented.
Claims (14)
1. The high-temperature-resistant catalyst is characterized by comprising an active component, an auxiliary agent and a carrier, wherein the active component is ruthenium, the auxiliary agent is titanium, and the carrier is alumina or silica pretreated by coal water slurry;
the preparation method of the catalyst comprises the following steps:
(1) preparing an impregnation solution, wherein the solution contains: an active component precursor, an auxiliary agent precursor, citric acid and glycol;
(2) uniformly mixing the pre-carrier and the water-coal-slurry solution, transferring the mixture into a high-pressure reaction kettle, and reacting for 3-5 hours at the temperature of 500-800 ℃ and under the pressure of 2-4 MPa in a reducing atmosphere;
(3) filtering the reaction mixture obtained in the step (2), drying the obtained solid sample, and roasting at 600-1000 ℃ for 2-4 h to obtain a carrier;
(4) and (3) impregnating the carrier obtained in the step (3) with the impregnation solution obtained in the step (1), drying, and roasting in a reducing atmosphere II to obtain the catalyst.
2. The catalyst according to claim 1,
in the step (1), the concentration of the active component precursor is 0.5-2 g/100mL based on ruthenium, the concentration of the auxiliary agent precursor is 0.05-0.2 g/100mL based on titanium, the concentration of citric acid is 0.3-2.8 g/100mL, and the concentration of ethylene glycol is 0.5-3.4 g/100 mL.
3. The catalyst of claim 1, wherein: the active component precursor in the step (1) is one or more of ruthenium trichloride, ruthenium acetate, ruthenium acetylacetonate and ruthenium dodecacarbonyl; the auxiliary agent precursor is one or more of titanium tetrachloride, titanium trichloride, titanocene dichloride and tetrabutyl titanate.
4. The catalyst of claim 1, wherein: the ruthenium is selected from ruthenium trichloride or ruthenium acetate; the titanium is selected from titanium trichloride or titanocene dichloride.
5. The catalyst of claim 1, wherein: the preparation method of the impregnation liquid in the step (1) comprises the steps of sequentially dropwise adding an active component precursor and an auxiliary agent precursor into an aqueous solution, heating to 40-80 ℃, then sequentially adding citric acid and ethylene glycol, and stirring at a constant temperature for 1-2 hours.
6. The catalyst of claim 5, wherein: the dropping speed of the active component precursor is 0.5-2mL/min, the dropping speed of the auxiliary agent precursor is 0.1-0.6mL/min, and the stirring speed at constant temperature is 100-300 rpm.
7. The catalyst of claim 1, wherein: in the step (2), the pre-carrier is any one of alumina or silicon oxide; the concentration of the coal water slurry is 58-68%, and the viscosity of the coal water slurry is 700-1400 mPa.s; the mass ratio of the pre-carrier to the coal water slurry is 1: 1-5: 1.
8. The catalyst of claim 7, wherein: the concentration of the coal water slurry is 60% -65%, and the viscosity of the coal water slurry is 850-1200 mPa.s.
9. The catalyst of claim 1, wherein: the reducing atmosphere I in the step (2) is a mixed gas of carbon monoxide and nitrogen or a mixed gas of hydrogen and nitrogen, and the volume percentage of the nitrogen in the mixed gas is 5-90%.
10. The catalyst of claim 9, wherein: the volume percentage of nitrogen in the mixed gas is 40-70%.
11. The catalyst of claim 1, wherein: the impregnation process in the step (4) adopts equal-volume impregnation, the impregnation time is 6-10 h, the drying temperature is 80-180 ℃, the drying time is 4-8 h, the roasting temperature is 800-1300 ℃, and the roasting time is 1-2 h.
12. The catalyst of claim 1, wherein: and (4) the reducing atmosphere II in the step (4) is a mixed gas of hydrogen and carbon monoxide, and the volume percentage of the hydrogen in the mixed gas is 30-50%.
13. Use of a catalyst according to any one of claims 1 to 12, wherein: the catalyst is used as a coal water slurry additive to be applied to a gasification furnace to catalyze synthesis gas to generate formic acid.
14. The use of claim 13, wherein the amount of catalyst added is 0.01% to 2% of the total mass of the coal water slurry.
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| CN112965386B (en) * | 2021-02-22 | 2022-03-15 | 上海交通大学 | Coal water slurry gasification and coal-fired boiler ultra-low NOx emission integrated cooperative control method |
| CN117138775B (en) * | 2023-07-24 | 2024-04-30 | 昆明贵金属研究所 | Catalytic system for preparing formic acid by catalyzing carbon dioxide hydrogenation under alkali-free condition |
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| US7030053B2 (en) * | 2002-11-06 | 2006-04-18 | Conocophillips Company | Catalyst composition comprising ruthenium and a treated silica support component and processes therefor and therewith for preparing high molecular weight hydrocarbons such as polymethylene |
| CN101279271B (en) * | 2007-04-06 | 2010-09-29 | 中国石油天然气股份有限公司 | Catalyst for producing synthesis gas by catalytic partial oxidation of methane and preparation thereof |
| CN103864597B (en) * | 2014-03-27 | 2015-10-21 | 西安科技大学 | The application that a kind of loading type Ru is catalyst based |
| CN108057438A (en) * | 2017-09-06 | 2018-05-22 | 贵研工业催化剂（云南）有限公司 | It is a kind of to prepare ruthenium catalyst of hydrogen peroxide and preparation method thereof for anthraquinone hydrogenation |
| CN109453763B (en) * | 2017-09-06 | 2021-06-01 | 中国石化扬子石油化工有限公司 | Catalyst for preparing 1, 4-butanediol by aqueous phase hydrogenation of succinic acid and preparation method thereof |
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