CN113083282B - Composite metal desulfurization catalyst with double functions of conversion and absorption and preparation method thereof - Google Patents
Composite metal desulfurization catalyst with double functions of conversion and absorption and preparation method thereof Download PDFInfo
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
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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
- B01J23/70—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
- B01J23/80—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 zinc, cadmium or mercury
Abstract
The invention discloses a composite metal desulfurization catalyst with double functions of conversion and absorption and a preparation method thereof, belonging to the technical field of catalyst desulfurization and purification. The catalyst has the capability of simultaneously converting organic sulfur and adsorbing and removing sulfides, and particularly, the organic sulfur which is difficult to remove by a conventional method is converted into inorganic sulfur, and then is simultaneously adsorbed and removed with the inorganic sulfur contained in an air source. In the preparation aspect, the utilization rate of the metal salt is improved by using a precipitation method, the cost is saved, the catalyst with more uniform active component dispersibility is obtained, and the catalyst has good conversion desulfurization capability within the temperature range of 250-350 ℃, high selectivity and low cost.
Description
Technical Field
The invention relates to the technical field of catalytic desulfurization of catalysts and preparation of catalysts, in particular to a composite metal desulfurization catalyst with conversion and absorption functions and a preparation method thereof, which are applied to removal of impurity gases such as inorganic sulfur, organic sulfur and the like contained in various fossil fuel gases.
Background
Sulfides are widely present in fossil fuel gases such as blast furnace gas, coke oven gas, petroleum gas, natural gas and the like, and the presence of the sulfides not only pollutes the environment, but also can cause catalyst poisoning in the subsequent production process, product quality is reduced, and equipment is corroded. The sulfide is mainly inorganic sulfur (more than 90% of H) 2 S) and organic sulfur (COS, CS) 2 Mercaptans, etc.) because COS is greater than H 2 S has much less chemical activity and weaker acidity and polarity than H 2 S, so are generally used for removing H 2 The method of S can not effectively and completely remove COS, and the hydrodesulfurization method is a more appropriate method in the field of high-efficiency removal of organic sulfur at present, and the reaction equation is as follows: COS + H 2 → CO+H 2 S and CS 2 +2H 2 +CO 2 → 2CO+2H 2 S, the essence of hydrodesulfurization is that COS/CS is desulfurized by a dual-functional composite metal desulfurization catalyst 2 Conversion to H 2 S, since fossil fuel gas itself also contains a certain amount of inorganic sulfur (over 90% H) 2 S), so organic sulfur can be first converted into H 2 S, the zinc oxide catalyst in the composite metal desulfurization catalyst can efficiently remove H 2 And S. However, the prior bifunctional hydrodesulfurization catalyst has the problems of low organic sulfur conversion rate, high cost, easy inactivation of the catalyst, high energy consumption due to the requirement of higher working temperature and the like.
The semi-coke is used as a novel carbon material, has the advantages of high fixed carbon, good adsorbability, high chemical activity, low ash content, high specific surface area, low sulfur content, low price and the like, and is widely applied to the production of products such as calcium carbide, ferroalloy, ferrosilicon, silicon carbide and the like by gradually replacing metallurgical coke and is used as a carrier for tail gas purification and the like.
Commercial alumina is the most widely used type of catalyst support, representing approximately 70% of commercially supported catalysts. Alumina has various forms, not only has different properties in different forms, but also has different properties such as density, pore structure, specific surface area and the like in the same form due to different sources, and is widely applied to the fields of petrochemical industry, hydrodesulfurization, sulfur resistance reduction, water treatment, flue gas adsorption and the like.
Chinese patent CN104740994A discloses a high-concentration carbonyl sulfide conversion-absorption type desulfurizer prepared from magnetic iron oxide, anatase type and alkali metal oxide K 2 O and a binder. A large amount of acidic solution is needed for adjustment in the preparation process, the cost is too high, and the industrial amplification cannot be realized.
In summary, the conventional desulfurization catalyst developed at present has certain problems in the aspects of energy consumption, selectivity, conversion rate and the like, so that the bifunctional composite metal desulfurization catalyst capable of meeting deep desulfurization is developed, can convert organic sulfur into inorganic sulfur at 200-300 ℃ and simultaneously remove the inorganic sulfur, and has the advantages of high conversion rate, long service life, good selectivity and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite metal desulfurization catalyst with double functions of conversion and absorption, and the catalyst has the advantages of high conversion rate, high removal rate, low removal cost and high efficiency, and is suitable for industrial amplification use.
Therefore, the invention provides the following technical scheme.
The preparation method of the composite metal desulfurization catalyst with double functions of conversion and absorption is characterized by comprising the following steps:
1) Respectively immersing the carrier into a composite metal salt solution containing zinc ions and other metal ions and a zinc ion salt solution, respectively adding an alkaline solution to control the pH values of the two solutions so that the metal ions form corresponding precipitated compounds, and precipitating the precipitated compounds on the surface of the carrier and in a pore channel to obtain two corresponding products;
2) Respectively placing the two products obtained in the step 1) in a drying oven for drying, and then placing in a box-type furnace for roasting at a certain high temperature to obtain a catalyst I simultaneously loaded with zinc oxide and other metal oxides and a catalyst III only loaded with zinc oxide;
3) Combining the catalyst I obtained in the step 2) with a catalyst III to obtain the composite metal desulfurization catalyst with double functions of conversion and absorption.
Furthermore, the invention also limits that the metal in the other metal ions is Mo or Ni.
Further, the invention also limits the carrier to be semi-coke and commercial alumina.
Furthermore, the invention also defines that the corresponding precursor of the metal oxide is metal nitrate.
Further, the invention also defines that the alkaline solution is any one of saturated sodium carbonate solution and saturated sodium bicarbonate solution, and preferably saturated sodium carbonate solution.
Furthermore, the invention also limits the pH value to be controlled between 8 and 13.
Further, the invention also defines that the mixture is placed in an oven to be dried for 4 to 8 hours at the temperature of 80 to 140 ℃ after being kept still for 12 hours after the loading is finished by a precipitation method, and is preferably dried for 6 hours at the temperature of 120 ℃.
Further, the invention also limits that the mixture is placed in a box type furnace for roasting and oxidizing after the drying is finished, wherein the roasting and oxidizing temperature is 200-600 ℃, preferably 300-500 ℃, and the roasting and oxidizing time is 1-6 hours, preferably 2-5 hours.
Further, the present invention also defines a dual-function composite metal desulfurization catalyst for conversion and absorption, which is prepared by the method of any one of claims 1 to 8.
The catalyst is as follows: the catalyst I and the catalyst III are directly and physically mixed according to a certain ratio (1.
In the catalyst I, the weight percentages of the carrier and the metal salt are as follows:
carrier: 90 to 99.5 percent
Other metal salts, zinc salts: 0.5% -10% (the charge ratio of other metal salts to zinc salts is 1
In catalyst III, the weight percentages of the carrier and the metal salt are as follows:
carrier: 90 to 99.5 percent
Zinc salt: 0.5 to 10 percent
The bifunctional desulfurization catalyst is prepared by adopting a precipitation method, and the preparation method comprises the following specific steps:
(1) Taking a precursor nitrate of the metal oxide at room temperature: molybdenum nitrate, nickel nitrate and zinc nitrate. Dissolving a proper amount of molybdenum nitrate and nickel nitrate and zinc nitrate in deionized water with a fixed volume according to different mass ratios to obtain solutions of molybdenum nitrate and zinc nitrate and nickel nitrate and zinc nitrate respectively, and then placing the solutions in ultrasonic for ultrasonic treatment for 30min to fully dissolve and uniformly disperse the solutions to obtain 3 parts of different nitrate solutions.
(2) Taking a carrier with a certain mass, wherein the carrier is commercial alumina or semi coke, washing the carrier with deionized water to remove ash and impurities on the surface and expose blocked pore channels so as to facilitate later-stage loading of oxidation state metal, then placing the washed carrier in a drying oven, drying for a certain time at 120 ℃, and taking out the carrier for later use after drying.
(3) And (2) dividing the 3 saturated nitrate solutions obtained in the step (1) into two parts to obtain 3 solutions, wherein 6 parts of the 3 solutions are obtained, 15g of treated semi-coke or commercial alumina is added into the 3 solutions respectively, and then the ultrasonic treatment is carried out for 15min.
(4) While stirring, a certain amount of saturated sodium carbonate solution is dropwise added into 6 parts of the solution, so that the precipitate is clearly seen to be continuously generated in the solution, the precipitate is uniformly dispersed on the carrier by stirring, and after the precipitate is completely precipitated, the solution is kept stand at room temperature for 12 hours.
(5) Putting the product obtained in the step (4) into an oven, drying for 6h at 120 ℃, putting the dried product into a box-type furnace, and roasting at 200-600 ℃, wherein the preferred roasting temperature is 300-500 ℃; the calcination time is 1-6h, preferably 2-5h.
(6) After the baking and sintering are finished, the temperature of the catalyst is naturally reduced, wherein the catalyst I and the catalyst II are respectively and uniformly mixed with the catalyst III according to the proportion of 1.
The activity test of the bifunctional desulfurization catalyst is carried out in a fixed bed reactor, the catalyst to be tested is placed in a fixed bed quartz tube adsorption column by a certain mass, and an experiment is carried out by using a mixed gas source to simulate industrial sulfur-containing gas (wherein H is H) 2 S/COS/CS 2 The concentrations are all 500mg/m 3 The residual gas is N 2 :94%、H 2 :2%、CO 2 2% and 2% CO), the mixed simulated gas enters the flow meter from the gas steel cylinder through the pressure reducing valve, enters the fixed bed adsorption unit at a certain gas flow rate, the high-efficiency removal process of the organic sulfur is carried out in a quartz tube adsorption column, the temperatures of the heating furnace and the adsorption column are controlled by a program temperature controller and a temperature controller together with a thermocouple, the organic sulfur concentration of the inlet and outlet gas is analyzed and detected in real time by using a professional gas chromatography instrument provided with an FPD detector.
10g of the bifunctional desulfurization catalyst was placed in a fixed bed quartz tube adsorption column having an inner diameter of 2cm, the column height of the hydrogenation catalyst was about 6cm, the porosity of the semi-coke (commercial alumina) catalyst was about 30% (18%), the reaction temperature was 250-350 ℃, the flow rate of the mixed simulated gas was 500mL/min, and the activity of the hydrogenation catalyst was expressed as the organic sulfur removal rate in a fixed time.
The reagents used in the preparation process of the catalyst are all analytically pure.
Compared with the prior art, the bifunctional composite metal desulfurization catalyst has the following advantages:
the bifunctional desulfurization catalyst has high conversion rate to organic sulfur and good selectivity, can fully convert the organic sulfur into inorganic sulfur, and can simultaneously remove the inorganic sulfur contained in an air source and the converted inorganic sulfur because the bifunctional desulfurization catalyst has extremely excellent absorption and combination properties to the inorganic sulfur. And the semi-coke or commercial alumina carrier is used during preparation, and the carrier is low in price and wide in source, so that the method is very suitable for industrial desulfurization application.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The invention provides a composite metal desulfurization catalyst with double functions of conversion and absorption.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Weighing 1000g of semi-coke and commercial alumina, respectively placing the semi-coke and the commercial alumina in 2000mL of deionized water for washing, washing away ash and impurities on the surface of a carrier, exposing a blocked pore channel, facilitating later-stage metal ion loading modification, then placing the cleaned carrier in a drying oven, drying for a certain time at 120 ℃, and taking out the carrier for later use after drying.
Weighing a certain mass of zinc nitrate, molybdenum nitrate, nickel nitrate and sodium carbonate respectively, and preparing a saturated zinc nitrate solution, a mixed solution of zinc nitrate and molybdenum nitrate, a mixed solution of zinc nitrate and nickel nitrate and a sodium carbonate solution respectively.
Example 1: semi-coke bifunctional desulfurization catalyst for loading different composite metals
Weighing 5 parts of 15g of treated semi coke, respectively adding 5 parts of saturated (1) zinc nitrate solution, (2) zinc nitrate solution, (3) zinc nitrate solution, (4) zinc nitrate and molybdenum nitrate mixed solution, and (5) zinc nitrate and nickel nitrate mixed solution, uniformly mixing by ultrasonic treatment, dropwise adding sodium carbonate solution into the solution by using a constant-pressure dropping funnel at normal temperature while stirring, stopping dropwise adding the solution when the pH value reaches 10-11, starting to stand for 10h, drying in an oven at 120 ℃ for 6h after standing, roasting in a box furnace at 350 ℃ for 4h after drying, and taking 5 parts of product after roasting is finished and naturally cooled, wherein three parts are a desulfurization catalyst III only loaded with zinc oxide, and the rest two parts are a desulfurization catalyst I loaded with zinc nitrate and molybdenum nitrate and a desulfurization catalyst II loaded with zinc nitrate and nickel nitrate.
Mixing two parts of composite metal desulfurization catalyst I and catalyst II which load zinc nitrate and molybdenum nitrate and zinc nitrate and nickel nitrate with two parts of desulfurization catalyst III which only load zinc oxide according to the proportion of 1:
catalyst No. 1 [ Mo-Zn/Zn @ AC ] and catalyst No. 2 [ Ni-Zn/Zn @ AC ].
The remaining part of the desulfurization catalyst III only loaded with zinc oxide is: catalyst No. 3 [ Zn @ AC ].
The conversion desulfurization performance of the catalyst 1, the catalyst 2 and the catalyst 3 prepared in example 1 was tested in turn by using a fixed bed, 10g of the catalysts were placed in a fixed bed quartz tube having an inner diameter of 2cm, the column height of the catalyst was about 6cm, the reaction temperature of the catalyst in the fixed bed was 280 ℃, the flow rate of the mixed simulated gas was 500mL/min, and a COS standard gas (wherein H) was used in the experimental test (see fig. 1) 2 S/COS/CS 2 The concentrations are all 500mg/m 3 Is left overThe residual gas being N 2 :94%、H 2 :2%、CO 2 2 percent and 2 percent of CO), the testing time is 24 hours, the total content of sulfide in the tail gas is detected and analyzed every 10 minutes by the chromatogram of the tail gas after being converted and removed by the fixed bed, and the average sulfide removal rate of 6 times in the last 1 hour is taken as the removal rate of the catalyst for the performance evaluation of the catalyst.
Through experimental detection, when the fixed carriers of the catalysts No. 1, no. 2 and No. 3 are semi-coke, the loading amount is 2%, the roasting activation temperature is 350 ℃, and the working temperature is 280 ℃, and the evaluation time is 24 hours, the 6-time average sulfide removal rates of the last 1 hour of the catalysts No. 1, no. 2 and No. 3 are 96.172%, 93.538% and 78.691% respectively.
For catalyst No. 3, the supported zinc oxide active component is on H 2 S has an excellent removal rate but has a relatively poor removal rate of COS, and since Zn and COS have a weaker binding energy than Mo and COS, the catalyst supporting a single metal has a poorer performance than the other two composite metal catalysts.
Example 2: bifunctional desulfurization catalyst for commercial alumina when loading different composite metals
Weighing 3 parts of 15g of treated commercial alumina, respectively adding a saturated zinc nitrate solution, a mixed solution of zinc nitrate and molybdenum nitrate and a mixed solution of zinc nitrate and nickel nitrate which are prepared in advance, uniformly mixing by ultrasonic treatment, dropwise adding a sodium carbonate solution into the solution by using a constant-pressure dropping funnel under stirring at normal temperature, stopping dropwise adding the solution when the pH value reaches 10-11, standing for 10 hours, drying in an oven at 120 ℃ for 6 hours after standing, and roasting in a box furnace at 350 ℃ for 4 hours after drying.
After baking and sintering, taking out a product after the product is naturally cooled, and mixing two parts of composite metal desulfurization catalysts I and II loaded with zinc nitrate and molybdenum nitrate and zinc nitrate and nickel nitrate with a desulfurization catalyst III loaded with zinc oxide only according to the proportion of 1:
catalyst No. 1 [ Mo-Zn/Zn @ ] Al 2 O 3 ]With catalyst No. 2 [ Ni-Zn/Zn @ ] Al 2 O 3 ]。
The conversion removal performance of the catalyst No. 1 and the conversion removal performance of the catalyst No. 2 prepared in example 2 were tested in sequence by using a fixed bed, 10g of each catalyst was placed in a fixed bed quartz tube having an inner diameter of 2cm, the column height of the catalyst was about 6cm, the reaction temperature of the catalyst in the fixed bed was 280 ℃, the flow rate of the mixed simulated gas was 500mL/min, and a COS standard gas (H) was used in the experimental test (H is herein used as the COS standard gas) 2 S/COS/CS 2 The concentrations are all 500mg/m 3 The residual gas is N 2 :94%、H 2 :2%、CO 2 2 percent of CO and 2 percent of CO, the testing time of the catalyst No. 1 and the catalyst No. 2 is 24 hours, the total content of sulfide in the tail gas is detected and analyzed every 10 minutes by the chromatogram of the tail gas after being converted and removed by the fixed bed, and the performance evaluation of the catalyst takes the average sulfide removal rate of 6 times of the last 1 hour to represent the removal rate of the catalyst.
It was found through experimental detection that when the fixed carriers of catalysts No. 1 and No. 2 were commercial alumina, the supporting amount was 2%, the calcination activation temperature was 350 ℃, and the operating temperature was 280 ℃, the performance of both catalysts was 98.034% and 95.827% at an evaluation time of 24 hours.
Example 3: influence of different zinc oxide catalyst ratios on overall desulfurization performance
Weighing 2 parts of 30g of treated semi coke, respectively adding the semi coke into a saturated zinc nitrate solution and a mixed solution of zinc nitrate and molybdenum nitrate which are prepared in advance, uniformly mixing the semi coke through ultrasonic treatment, dropwise adding a sodium carbonate solution into the solution by using a constant-pressure dropping funnel under stirring at normal temperature, stopping dropwise adding the solution when the pH value reaches 10-11, starting standing for 10 hours, drying the semi coke in a drying oven at 120 ℃ for 6 hours after the standing is finished, and roasting the semi coke in a box furnace at 350 ℃ for 4 hours after the drying is finished.
After the baking and sintering, taking out a product after the product is naturally cooled, and mixing a desulfurization catalyst I loaded with the zinc nitrate and molybdenum nitrate composite metal and a desulfurization catalyst III loaded with the zinc oxide according to the proportion of 3, 2:
three parts of catalyst in different proportions [ Mo-Zn/Zn @ AC]The conversion removal performance of the catalyst prepared in example 3 was tested using a fixed bed in sequence, and eachSequentially taking 10g of catalyst, placing the catalyst in a fixed bed quartz tube with the inner diameter of 2cm, wherein the column height of the catalyst is about 6cm, the reaction temperature of the catalyst in the fixed bed is 280 ℃, the flow rate of a mixed simulation gas is 500mL/min, and adopting COS standard gas (wherein H is the same as the COS standard gas) used in an experimental test 2 S/COS/CS 2 The concentrations are all 500mg/m 3 The residual gas is N 2 :94%、H 2 :2%、CO 2 2 percent of CO and 2 percent of CO), the testing time of the catalyst is 24 hours, the total content of sulfide in the tail gas after the tail gas is converted and removed by the fixed bed is detected and analyzed every 10 minutes by a chromatograph, and the performance evaluation of the catalyst takes the average sulfide removal rate of 6 times of the last 1 hour to represent the removal rate of the catalyst.
Experimental detection shows that when the fixed carrier of the catalyst is semi-coke, the loading capacity is 2%, the roasting activation temperature is 350 ℃, and the working temperature is 280 ℃, and the evaluation time is 24 hours, the performances of the three catalysts with different proportions are 96.172%, 97.749% and 95.591%.
It was found through experimental comparison that when the composite metal desulfurization catalyst No. i and the desulfurization catalyst No. iii supporting only zinc oxide were mixed in a ratio of 3.
Example 4: effect of reaction temperature on the Performance of a blue-carbon based Zinc/molybdenum desulfurization catalyst
Respectively weighing 2 parts of 30g of treated semi coke, respectively adding the semi coke into a saturated zinc nitrate solution and a mixed solution of zinc nitrate and molybdenum nitrate which are prepared in advance, uniformly mixing the semi coke through ultrasonic treatment, then dropwise adding a sodium carbonate solution into the solution by using a constant-pressure dropping funnel while stirring at normal temperature, stopping dropwise adding the solution when the pH value reaches 10-11, starting to stand for 10 hours, placing the solution in a drying oven to dry for 6 hours at 120 ℃ after standing, roasting for 4 hours at 350 ℃ in a box type oven after drying, taking out a product after naturally cooling the product after roasting, and mixing a zinc nitrate and molybdenum nitrate loaded composite metal desulfurization catalyst I and a desulfurization catalyst III only loaded with zinc oxide according to the proportion of 2: catalyst [ Mo-Zn/Zn @ AC ].
The conversion and removal performance of the catalyst prepared in example 4 was tested in turn using a fixed bed, 10g of the catalyst was placed in a fixed bed quartz tube with an inner diameter of 2cm, the column height of the catalyst was about 6cm, the reaction temperature of the catalyst in the fixed bed was 230 ℃, 280 ℃, 330 ℃, the flow rate of the mixed simulated gas was 500mL/min, and the COS standard gas (H) was used in the experimental test (H is a gas containing hydrogen, carbon monoxide, hydrogen, and hydrogen), which was used in the experiment 2 S/COS/CS 2 The concentrations are all 500mg/m 3 The residual gas is N 2 :94%、H 2 :2%、CO 2 2 percent of catalyst and 2 percent of CO, the testing time of the catalyst is 24 hours, the total content of sulfide in the tail gas is detected and analyzed every 10 minutes by the chromatogram of the tail gas after being converted and removed by the fixed bed, and the average sulfide removal rate of 6 times in the last 1 hour is taken as the removal rate of the catalyst for the performance evaluation of the catalyst.
Through experimental detection, when the fixed carrier of the catalyst is semi-coke, the loading amount is 2%, the roasting activation temperature is 350 ℃, the working temperature is 230 ℃, 280 ℃ and 330 ℃, and the evaluation time is 24 hours, the performances of the three catalysts at different working temperatures are 82.647%, 97.749% and 97.623%.
Through comparison of example 4, it is found that when the catalyst shows different performances at different working temperatures, the removal rate is low due to incomplete conversion of organic sulfur at the relatively slightly low working temperature, but the excessive temperature has little effect on improving the performances, and the energy consumption is comprehensively considered, so that the working temperature of the catalyst is most suitable to be 280 ℃ for the three different working temperatures in example 4.
Example 5: desulfurization performance of semi-coke loaded single metal oxide
Weighing 3 parts of 30g of treated semi coke, respectively adding a zinc nitrate solution, a molybdenum nitrate solution and a nickel nitrate solution which are prepared in advance according to a 2% loading capacity, uniformly mixing the materials through ultrasonic treatment, dropwise adding a sodium carbonate solution into the solution by using a constant-pressure dropping funnel under stirring at normal temperature, stopping dropwise adding the solution when the pH value reaches 10-11, standing for 10 hours, drying the solution in a drying oven at 120 ℃ for 6 hours after standing, roasting the solution in a box type furnace at 350 ℃ for 4 hours after drying, and taking out the product after roasting and naturally cooling the product.
Respectively naming the semi-coke catalyst loaded with zinc nitrate, molybdenum nitrate and nickel nitrate as follows: (1) [ Zn @ AC ], (2) [ Mo @ AC ], (3) [ Ni @ AC ].
The conversion removal performance of the three catalysts prepared in example 5 was tested in sequence by using a fixed bed, 10g of each catalyst was placed in a quartz tube with an inner diameter of 2cm in sequence, the column height of the catalyst was about 6cm, the reaction temperature of the catalyst in the fixed bed was 280 ℃, the mixing simulation air flow rate was 500mL/min, and COS standard gas (wherein H is used in the experimental test) was adopted 2 S/COS/CS 2 The concentrations are all 500mg/m 3 The residual gas is N 2 :94%、H 2 :2%、CO 2 2 percent and 2 percent of CO), the testing time of the catalyst is 24 hours, the components and the content of the sulfide in the tail gas after the tail gas is converted and removed by the fixed bed are regularly detected and analyzed every 10 minutes by gas chromatography, and the performance evaluation of the catalyst takes the average sulfide removal rate of 6 times of the last 1 hour to represent the removal rate of the catalyst.
Through experimental detection, when the fixed carrier of the catalyst is semi-coke, the loading amount is 2%, the roasting activation temperature is 350 ℃, and the working temperature is 280 ℃, and the evaluation time is 24 hours, the performances of three catalysts in example 5 are shown in table 1:
Claims (9)
1. a preparation method of a composite metal desulfurization catalyst with double functions of conversion and absorption is characterized by comprising the following steps:
1) Respectively immersing a carrier into a composite metal salt solution containing zinc ions and other metal ions and a zinc ion salt solution, respectively adding an alkaline solution to control the pH values of the two solutions so that the metal ions form corresponding precipitated compounds, and attaching the precipitated compounds to the surface and in a pore channel of the carrier to obtain two corresponding products;
2) Respectively placing the two products obtained in the step 1) in a drying oven for drying, and then placing in a box-type furnace for roasting and activating at a certain high temperature to obtain a catalyst I simultaneously loaded with zinc oxide and other metal oxides and a catalyst III only loaded with zinc oxide;
in the catalyst I, the weight percentage contents of the carrier and the metal salt are as follows:
carrier: 90% -99.5%; other metal salts, zinc salts: 0.5% -10%;
in catalyst III, the weight percentage of the carrier and the metal salt is as follows:
carrier: 90% -99.5%; zinc salt: 0.5 to 10 percent;
3) Mechanically mixing the catalyst I obtained in the step 2) with the catalyst III to obtain the composite metal desulfurization catalyst with double functions of conversion and absorption, wherein the catalyst I is used for converting organic sulfur into inorganic sulfur, and the catalyst III is used for removing the inorganic sulfur.
2. The method for preparing a dual-function composite metal desulfurization catalyst for conversion and absorption according to claim 1, wherein: the metal in the other metal ions is Mo or Ni.
3. The method for preparing a dual-function composite metal desulfurization catalyst for conversion and absorption according to claim 1, wherein: the carrier is semi-coke and commercial alumina.
4. The method of claim 1 for preparing a dual function composite metal desulfurization catalyst for both conversion and absorption, comprising: the precursor corresponding to the metal oxide is metal nitrate.
5. The method of claim 1 for preparing a dual function composite metal desulfurization catalyst for both conversion and absorption, comprising: the alkaline solution is any one of saturated sodium carbonate solution and saturated sodium bicarbonate solution.
6. The method of claim 1 for preparing a dual function composite metal desulfurization catalyst for both conversion and absorption, comprising: the pH value is controlled to be 8-13.
7. The method for preparing a dual-function composite metal desulfurization catalyst for conversion and absorption according to claim 1, wherein: after loading by a precipitation method, standing for 12h, and drying in an oven at 80-140 ℃ for 4-8h.
8. The method of claim 1 for preparing a dual function composite metal desulfurization catalyst for both conversion and absorption, comprising: and after drying, placing the mixture in a box type furnace for roasting and oxidizing at the roasting and oxidizing temperature of 200-600 ℃ for 1-6h.
9. A dual function composite metal desulfurization catalyst for both conversion and absorption, characterized in that it is prepared by the process according to any one of claims 1 to 8.
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| CN109647484A (en) * | 2019-01-21 | 2019-04-19 | 西安理工大学 | A kind of preparation method of nanometer sheet/nanotube composite construction carbon nitride material |
| CN112058273A (en) * | 2020-08-26 | 2020-12-11 | 中国科学院山西煤炭化学研究所 | Blast furnace gas desulfurization catalyst and preparation method and application thereof |
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| CN109647484A (en) * | 2019-01-21 | 2019-04-19 | 西安理工大学 | A kind of preparation method of nanometer sheet/nanotube composite construction carbon nitride material |
| CN112058273A (en) * | 2020-08-26 | 2020-12-11 | 中国科学院山西煤炭化学研究所 | Blast furnace gas desulfurization catalyst and preparation method and application thereof |
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