CN109107616B - Regeneration method of deactivated methanation catalyst - Google Patents
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/045—Regeneration
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a regeneration method of an inactivated methanation catalyst, which comprises the steps of firstly carrying out a series of screening, charcoal burning, acid washing and alkali washing on the inactivated methanation catalyst to obtain an activated catalyst carrier, recycling the solution after acid washing to prepare a regenerated solution, modifying the regenerated solution by using the solution after alkali washing, dipping the activated catalyst carrier in the modified regenerated solution, drying, roasting, and cooling to normal temperature to obtain a new methanation catalyst, thereby realizing the regeneration of the methanation catalyst; the method realizes the recycling of the waste solution and solves the problem of environmental pollution of the heavy metal solution; the new methanation catalyst prepared by the regeneration process improves the utilization rate of metallic nickel, and has high mechanical strength, good thermal stability and good carbon deposition resistance.
Description
Technical Field
The invention belongs to the technical field of methanation reaction, and relates to a regeneration method of an inactivated methanation catalyst.
Background
The methanation reaction is a strong exothermic reaction, and a large amount of heat released by the high-concentration CO methanation reaction can cause the instantaneous overtemperature of the bed layer, so that the catalyst is sintered at high temperature and is inactivated; in addition, the carbon deposition reaction is also accompanied with the methanation reaction, a large amount of filamentous carbon is generated in catalyst micropores under the low-temperature condition, and when sufficient pressure is generated, catalyst particles are crushed, so that a catalyst framework is pulverized and inactivated; under the condition of high temperature, the methanation reaction equilibrium constant is gradually reduced along with the temperature rise under the control of thermodynamics, high-density flaky crystalline carbon is generated at a surprising speed, the activity of the catalyst surface is covered, and the methanation activity is reduced.
At present, the industrial deactivated methanation catalyst is generally recovered by a high-temperature pyrogenic process, the residue is discarded or paved, and a large amount of nickel oxide still remains in the residue, so that the recovery rate of precious metals is low, resources are wasted, and environmental pollution is easily caused.
Chinese patent CN103265394 adopts two methanation reactors connected in parallel to realize alternative operation of methanation reaction and catalyst carbon elimination regeneration reaction, but the temperature of the carbon elimination reaction is generally above 700 ℃, a large amount of heat is consumed in the reaction process to maintain the temperature of the reactor bed, and the catalyst can not be activated thoroughly; in the Chinese patent CN102451774, the nickel-based catalyst is regenerated by alkali washing and then acid washing, and the surface of the catalyst after acid washing is easier to deposit carbon, so that the inactivation speed of the regenerated methane catalyst is higher, and the solution after alkali washing and acid washing can form secondary pollution.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a regeneration method of the inactivated methanation catalyst, which realizes the regeneration of the methanation catalyst by utilizing an environment-friendly regeneration technology, improves the utilization rate of metallic nickel, and ensures that the prepared methanation catalyst has good activity and long service life.
The invention is realized by the following technical scheme:
a method for regenerating a deactivated methanation catalyst comprises the following operations:
1) screening the inactivated methanation catalyst to obtain the inactivated methanation catalyst with a regular mechanical structure, roasting the inactivated methanation catalyst in an air atmosphere, carrying out charcoal-burning treatment on the catalyst, and fully oxidizing metals contained in the catalyst to obtain corresponding metal oxides; using acid pickling solution to dissolve the metal oxide in the catalyst, separating the components losing the regeneration performance, and recovering the pore structure in the catalyst; then carrying out alkali washing treatment on the acid-washed catalyst solid by an alkali washing solution and roasting to obtain an activated catalyst carrier, obtaining an acid-washed metal salt solution after pickling the acid-washed catalyst solid by the acid-washing solution, and obtaining an alkali-washed metal salt solution after alkali washing the catalyst solid by the alkali washing solution;
2) respectively filtering the acid washing metal salt solution and the alkali washing metal salt solution to remove impurity solid particles in the solutions, adding a new active component into the acid washing metal salt solution to prepare a regenerated solution, and modifying the regenerated solution by using the alkali washing metal salt solution to make the regenerated solution alkalescent and realize the recycling of the solutions, wherein the solution after being impregnated can be recycled after being treated; and (3) soaking the activated catalyst carrier in the regeneration solution, drying the surface of the catalyst after soaking, performing high-temperature treatment after drying, and cooling to normal temperature to obtain the regenerated methanation catalyst.
The carbon burning treatment is to screen the inactivated methanation catalyst, roast the inactivated methanation catalyst with a regular mechanical structure in an air atmosphere at 400-600 ℃ for 2-10 hours to fully burn carbon, and cool.
The acid washing solution is an acid solution prepared from one or more of acetic acid, citric acid, oxalic acid and nitric acid, preferably acetic acid and citric acid, and the catalyst solid is impregnated, wherein the mass percentage concentration of the acid washing solution is 0.8-1.2%, and the volume ratio of the acid washing solution to the catalyst solid is 5-8: 1.
The alkaline washing solution is one or more of sodium carbonate, sodium bicarbonate, ammonia water and ammonium bicarbonate to prepare an alkaline solution, preferably the ammonia water and the ammonium bicarbonate, and the catalyst solid is soaked, wherein the mass percentage concentration of the alkaline washing solution is 5-15%, and the volume ratio of the alkaline washing solution to the catalyst solid is 8-10: 1.
The regeneration solution is a mixed solution with nickel ion concentration of 3.0-3.5 mol/L and magnesium concentration of 1.0-1.5 mol/L; the volume ratio of the activated catalyst carrier to the regeneration solution is 10-15: 1.
The regeneration solution is a mixed solution of nickel nitrate and magnesium nitrate, and the activated catalyst carrier is placed in the regeneration solution to be soaked for 12-24 hours at the temperature of 80 ℃.
And after the impregnation is finished, spin-drying the impregnation liquid on the surface of the catalyst, drying at 80-120 ℃ for 4-6 h, roasting at 450-650 ℃ for 4-6 h in a nitrogen atmosphere, and cooling to normal temperature to obtain the regenerated methanation catalyst.
The regeneration method of the deactivated methanation catalyst specifically comprises the following operations:
1) screening the inactivated methanation catalyst to obtain an inactivated methanation catalyst with a regular mechanical structure, roasting for 2-10 hours at 400-600 ℃ in an air atmosphere to fully burn charcoal, then soaking in an acid washing solution with the concentration of 0.8-1.2% at 80 ℃ for 12-24 hours, spin-drying, then soaking and washing for 4-12 hours in an alkali washing solution with the concentration of 5-15% at 80 ℃, drying for 12-24 hours at 80-120 ℃ in an air atmosphere after spin-drying, roasting for 4-8 hours at 500-700 ℃ to prepare an activated methanation catalyst carrier, obtaining an acid washing metal salt solution after acid washing of the acid catalyst solid in the solution, and obtaining an alkali washing metal salt solution after alkali washing of the catalyst solid in the alkali washing solution;
2) respectively filtering the acid washing metal salt solution and the alkali washing metal salt solution to remove impurity solid particles, adding active components into the acid washing solution to prepare a mixed regeneration solution with the nickel ion concentration of 3.0-3.5 mol/L and the magnesium concentration of 1.0-1.5 mol/L, regulating the pH of the regeneration solution to 7.5-8 by using the alkali washing solution, soaking the activated catalyst carrier in the regeneration solution at 80 ℃ for 12-24 hours, drying the surface of the catalyst after the soaking is finished, drying the catalyst at 80-120 ℃ for 4-6 hours under the air atmosphere, roasting the catalyst for 4-6 hours under the inert atmosphere at 450-650 ℃, and cooling the catalyst to the normal temperature to obtain the regenerated methanation catalyst.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the regeneration method of the inactivated methanation catalyst, all the solutions after acid washing and alkali washing are recycled, so that the problem of serious environmental pollution is solved, the utilization rate of metallic nickel is improved, and zero emission in the preparation process of the catalyst is realized; the carrier of the regenerated methanation catalyst is subjected to long-term high-temperature test and is recycled after activation treatment, so that the methanation catalyst is high in mechanical strength, good in thermal stability, strong in carbon deposition resistance and sintering resistance, suitable for a complete methanation process of hydrogen and carbon monoxide under different working conditions, particularly suitable for a process technology for synthesizing natural gas by using coal to prepare gas, and also suitable for a process technology for preparing natural gas by using coke oven gas.
The comparative test shows that the activity of the regenerated methanation catalyst is compared with that of the fresh methanation catalyst, the regenerated methanation catalyst has good activity and thermal stability under the high-temperature condition, and can replace or partially replace the fresh methanation catalyst in actual production, so that the high-efficiency utilization of resources is realized.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
1) Screening the inactivated methanation catalyst to obtain an inactivated methanation catalyst with a regular mechanical structure, placing the inactivated methanation catalyst in an air atmosphere at 450 ℃ for roasting for 8 hours to fully burn charcoal, weighing 200g of the methanation catalyst, soaking and washing the methanation catalyst in 5 times of volume of nitric acid solution at 80 ℃ for 12 hours, soaking and washing the nitric acid solution at the mass percentage concentration of 0.8%, drying the nitric acid solution after drying for 4 hours in 8 times of volume of sodium bicarbonate solution at the mass percentage concentration of 15%, drying the dried methanation catalyst in the air atmosphere at 80 ℃ for 12 hours, roasting the methanation catalyst at 550 ℃ for 4 hours to prepare an activated catalyst carrier, pickling the acid catalyst in the acid solution for 4 hours to obtain a pickling metal salt solution, and washing the catalyst in the alkaline solution for 4 hours to obtain an alkaline washing metal salt solution;
2) respectively filtering the acid washing metal salt solution and the alkali washing metal salt solution to remove solid impurity particles, weighing 900g of nickel nitrate and 330g of magnesium nitrate to be dissolved in the acid washing metal salt solution to prepare a regenerated solution, weighing 1.5L of the alkali washing metal salt solution to adjust the pH value of the regenerated solution to be 7.5, soaking the activated catalyst carrier in the regenerated solution at 80 ℃ for 12 hours, spin-drying the surface of the catalyst after the soaking is finished, drying the catalyst at 80 ℃ for 6 hours under the air atmosphere, roasting the catalyst at 450 ℃ for 4 hours under the nitrogen atmosphere, and cooling the catalyst to the normal temperature to obtain the regenerated methanation catalyst.
Example 2
1) Screening the inactivated methanation catalyst to obtain an inactivated methanation catalyst with a regular mechanical structure, placing the inactivated methanation catalyst in an air atmosphere at 500 ℃ for roasting for 6 hours to fully burn charcoal, weighing 200g of the methanation catalyst from the inactivated methanation catalyst, soaking and washing the methanation catalyst in 5 times of oxalic acid solution at 80 ℃ for 12 hours, soaking and washing the oxalic acid solution in 10 times of sodium bicarbonate solution at 80 ℃ for 4 hours after spin-drying, drying the sodium bicarbonate solution at 80 ℃ for 12 hours in the air atmosphere after spin-drying, and roasting the mixture at 550 ℃ for 6 hours to obtain an activated catalyst carrier;
2) respectively filtering the metal salt solution subjected to acid washing and alkali washing to remove solid impurity particles, weighing 990g of nickel nitrate and 360g of magnesium nitrate, dissolving the nickel nitrate and the magnesium nitrate in the acid washing solution to prepare a regenerated solution, weighing 1.45L of the alkali washing solution to adjust the pH of the regenerated solution to 7.5, soaking the activated catalyst carrier in the regenerated solution at 80 ℃ for 12 hours, spin-drying the surface of the catalyst after soaking is finished, drying the catalyst at 80 ℃ for 6 hours under an air atmosphere, roasting the catalyst at 600 ℃ for 4 hours under a nitrogen atmosphere, and cooling the catalyst to the normal temperature to obtain the regenerated methanation catalyst.
Example 3
1) Screening the inactivated methanation catalyst to obtain an inactivated methanation catalyst with a regular mechanical structure, placing the inactivated methanation catalyst in an air atmosphere at 500 ℃ for roasting for 8 hours to fully burn charcoal, weighing 200g of the methanation catalyst, soaking and washing the methanation catalyst in a citric acid solution with 5 times of volume at 80 ℃ for 24 hours, soaking and washing the citric acid solution with the concentration of 1.2 percent at the temperature of 10 times of volume for 4 hours in an ammonium bicarbonate solution with the concentration of 12 percent at the temperature of 80 ℃ after spin-drying, drying the catalyst in the air atmosphere at the temperature of 80 ℃ for 12 hours, roasting the catalyst at 550 ℃ for 4 hours to prepare an activated catalyst carrier, pickling a pickling metal salt solution after pickling the acid catalyst in the acid catalyst solid solution, and an alkaline washing metal salt solution after the alkaline washing catalyst in the alkaline solution;
2) respectively filtering the acid-washing metal salt solution and the alkali-washing metal salt solution to remove solid impurity particles, weighing 930g of nickel nitrate and 307g of magnesium nitrate, dissolving the nickel nitrate and the magnesium nitrate in the acid-washing metal salt solution to prepare a regenerated solution, weighing 1.6L of the alkali-washing metal salt solution to adjust the pH value of the regenerated solution to 8, soaking the activated catalyst carrier in the solution at 80 ℃ for 12 hours, spin-drying the surface of the catalyst after soaking, drying the catalyst at 90 ℃ for 6 hours under an air atmosphere, roasting the catalyst at 550 ℃ for 4 hours under a nitrogen atmosphere, and cooling the catalyst to the normal temperature to obtain the regenerated methanation catalyst.
Example 4
1) Screening the inactivated methanation catalyst to obtain an inactivated methanation catalyst with a regular mechanical structure, roasting for 8 hours at 450 ℃ in an air atmosphere to fully burn charcoal, weighing 200g of the methanation catalyst, soaking and washing for 18 hours at 80 ℃ in 5 times of volume of acetic acid solution, soaking and washing for 1.1% of the acetic acid solution at 80 ℃ after spin-drying, soaking and washing for 6 hours at 80 ℃ in 10 times of volume of ammonia water solution at 15% of the ammonia water solution at 80 ℃ in an air atmosphere after spin-drying, roasting for 4 hours at 500 ℃ to obtain an activated catalyst carrier, obtaining an acid-washing metal salt solution after acid-washing solution acid catalyst solids, and obtaining an alkali-washing metal salt solution after alkali-washing catalyst solids in an alkali-washing solution;
2) respectively filtering the acid washing metal salt solution and the alkali washing metal salt solution to remove solid impurity particles, weighing 960g of nickel nitrate and 280g of magnesium nitrate, dissolving the nickel nitrate and the magnesium nitrate in the acid washing metal salt solution to prepare a regenerated solution, weighing 1.65L of the alkali washing metal salt solution, adjusting the pH value of the regenerated solution to 7.5, soaking the activated catalyst carrier in the regenerated solution at 80 ℃ for 12 hours, spin-drying the surface of the catalyst after the soaking is finished, drying the catalyst carrier at 100 ℃ for 4 hours in an air atmosphere, roasting the catalyst carrier at 650 ℃ for 4 hours in a nitrogen atmosphere, and cooling the catalyst carrier to the normal temperature to obtain the regenerated methanation catalyst.
Will be deactivatedThe methanation catalyst (2) is regenerated by the above method, its activity is evaluated and compared with the activity of a fresh methanation catalyst. The same evaluation conditions were used for both catalysts: respectively loading 10g of catalyst into a stainless steel reaction tube, and introducing the catalyst into the stainless steel reaction tube at a volume flow ratio of H2/N27, reduction space velocity 5000h-1Reducing for 8H at 600 ℃, and switching to H under the condition of mixed gas2: CO is 3:1, the pressure is 3MPa, and the space velocity is 20000h-1The reaction temperature is 300-;
the activity data for each example are shown in Table 1
Table 1 catalytic activity data
As can be seen from Table 1, compared with the activity of the fresh methanation catalyst, the activity and the thermal stability of the regenerated methanation catalyst are good, and the regenerated methanation catalyst can replace or partially replace the fresh methanation catalyst in actual production, so that the deactivated methanation catalyst can be reused.
The embodiments given above are preferable examples for implementing the present invention, and the present invention is not limited to the above-described embodiments. Any non-essential addition and replacement made by the technical characteristics of the technical scheme of the invention by a person skilled in the art belong to the protection scope of the invention.
Claims (5)
1. A method for regenerating a deactivated methanation catalyst, characterized in that it comprises the following operations:
1) screening the inactivated methanation catalyst to obtain the inactivated methanation catalyst with a regular mechanical structure, roasting the inactivated methanation catalyst in an air atmosphere, carrying out charcoal-burning treatment on the catalyst, and fully oxidizing metals contained in the catalyst to obtain corresponding metal oxides; pickling the catalyst solid with a pickling solution to dissolve metal oxides in the catalyst, separating components losing the regeneration performance, recovering the pore structure inside the catalyst, carrying out alkali washing treatment on the pickled catalyst solid with an alkali washing solution and roasting to obtain an activated catalyst carrier, pickling the catalyst solid with the pickling solution to obtain a pickling metal salt solution, and washing the catalyst solid with the alkali washing solution to obtain an alkali washing metal salt solution;
2) respectively filtering the acid washing metal salt solution and the alkali washing metal salt solution to remove impurity solid particles in the solutions, adding a new active component into the acid washing metal salt solution to prepare a regenerated solution, modifying the regenerated solution by using the alkali washing metal salt solution to make the regenerated solution alkalescent, soaking the activated catalyst carrier in the regenerated solution, spin-drying the surface of the catalyst after soaking is finished, drying, performing high-temperature treatment, and cooling to normal temperature to obtain a regenerated methanation catalyst;
the regeneration solution is a mixed solution with nickel ion concentration of 3.0-3.5 mol/L and magnesium concentration of 1.0-1.5 mol/L; the volume ratio of the activated catalyst carrier to the regeneration solution is 10-15: 1;
and after the impregnation is finished, spin-drying the impregnation liquid on the surface of the catalyst, drying at 80-120 ℃ for 4-6 h, roasting at 450-650 ℃ for 4-6 h in a nitrogen atmosphere, and cooling to normal temperature to obtain the regenerated methanation catalyst.
2. The process for regenerating a deactivated methanation catalyst as claimed in claim 1, characterized in that: the carbon burning treatment is to screen the inactivated methanation catalyst, roast the inactivated methanation catalyst with a regular mechanical structure in an air atmosphere at 400-600 ℃ for 2-10 hours to fully burn carbon, and cool.
3. The process for regenerating a deactivated methanation catalyst as claimed in claim 1, characterized in that: the acid washing solution is an acid solution prepared from one or more of acetic acid, citric acid, oxalic acid and nitric acid, wherein the mass percentage concentration of the acid washing solution is 0.8-1.2%, and the volume ratio of the acid washing solution to the catalyst solid is 5-8: 1.
4. The process for regenerating a deactivated methanation catalyst as claimed in claim 1, characterized in that: the alkaline washing solution is prepared from one or more of sodium carbonate, sodium bicarbonate, ammonia water and ammonium bicarbonate, wherein the mass percentage concentration of the alkaline washing solution is 5-15%, and the volume ratio of the alkaline washing solution to the catalyst solid is 8-10: 1.
5. The process for regenerating a deactivated methanation catalyst as claimed in claim 1, characterized in that: the regeneration solution is a mixed solution containing nickel nitrate and magnesium nitrate, and the activated catalyst carrier is placed in the regeneration solution to be soaked for 12-24 hours at the temperature of 80 ℃.
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| CN112221489A (en) * | 2020-11-18 | 2021-01-15 | 西安凯立新材料股份有限公司 | Regeneration method of gold carbon catalyst for preparing VCM |
| CN112517023B (en) * | 2020-12-30 | 2022-09-06 | 李通 | Recycling application method of inactivated non-noble metal chloroethylene catalyst carrier |
| CN114950578A (en) * | 2022-07-05 | 2022-08-30 | 江苏治水有数环保科技有限公司 | Catalyst regeneration process |
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| DE102008059202A1 (en) * | 2008-11-27 | 2010-06-10 | Highterm Research Gmbh | Regenerating a catalyst, whose catalytic activity is reduced by the adsorption of carbon, comprises irradiating the catalyst with the carbon deposition with high frequency electromagnetic waves for heating the carbon deposition |
| CN102451774A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for regenerating inactivated hydrotreating catalyst |
| CN103265394A (en) * | 2013-05-27 | 2013-08-28 | 神华集团有限责任公司 | Methanation reaction system and regeneration technology of methanation catalyst |
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