CN114471512A - Low-temperature methanation catalyst and preparation method thereof - Google Patents

Low-temperature methanation catalyst and preparation method thereof Download PDF

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CN114471512A
CN114471512A CN202011167741.0A CN202011167741A CN114471512A CN 114471512 A CN114471512 A CN 114471512A CN 202011167741 A CN202011167741 A CN 202011167741A CN 114471512 A CN114471512 A CN 114471512A
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low
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methanation catalyst
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王斌
展学成
孙利民
马好文
胡晓丽
陈明林
谢元
吕龙刚
梁顺琴
柏介军
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Petrochina Co Ltd
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Abstract

The invention provides low-temperature methanationThe catalyst is prepared from Ni as active component, carbon nanotube, diatomite and Al2O3Is a composite structure auxiliary agent, alkaline earth metal elements, rare earth elements and transition metal elements are modification auxiliary agents, and one or two of polyethylene glycol, sodium dodecyl benzene sulfonate or cellulose derivatives are dispersing agents. The catalyst is prepared by adopting a coprecipitation method, wherein the content of an active component Ni accounts for 30-75% of the total mass of the catalyst, the content of a composite structure auxiliary agent accounts for 20-60% of the total mass of the catalyst, the content of a modification auxiliary agent accounts for 0.5-15% of the total mass of the catalyst, and the content of a dispersing agent accounts for 0.1-5% of the total mass of the catalyst. The catalyst prepared by the invention can be used for a fixed bed reactor, and has good low-temperature activity and CO2High hydrogenation conversion rate.

Description

Low-temperature methanation catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a methanation catalyst with low-temperature activity and a preparation method thereof, belonging to the technical field of hydrogenation catalysts.
Background
The crude hydrogen gas in the ethylene industry plant and ammonia synthesis plant inevitably contains CO and CO2Components, the presence of which can have a toxic effect on downstream equipment and must therefore be cleaned. Purification of H in most of the existing plants2The methanation method is selected, namely, CO and CO are used2With a small amount of hydrogen to form inert CH4Removal of CO and CO from gases2。
The hydrogen-rich gas separated from the hydrogen/methane separation tank in the industrial device for preparing ethylene by cracking naphtha and light hydrocarbon inevitably contains CO and CO2And the part H2Is a feedstock for downstream hydrogenation processes and can cause catalyst poisoning and deactivation if the CO is not removed.
The reaction temperature of the catalyst generally used in the current ethylene industrial device is 280-350 ℃, and the reaction temperature of the catalyst for low-temperature methanation is 150-200 ℃. Before the raw gas enters the methanation reactor, high-pressure steam is needed to heat the raw gas so that the raw gas can meet the temperature required by the reaction. Contrast high temperature methanation catalyst, use the quantity of saving high-pressure steam that low temperature methanation catalyst can be very big, improve the factor of safety of operation, reduce the requirement to equipment, be difficult for initiating high temperature interlocking, simultaneously can energy saving and consumption reduction promotion economic benefits. Therefore, the development of the methanation catalyst used under the low-temperature condition has important significance and broad prospect.
At present, the domestic low-temperature methanation technology is not mature enough, and monopoly is carried out on the low-temperature methanation technology abroad, so that the development of a low-temperature methanation catalyst is necessary. CN108479844A discloses a CO low-temperature selective methanation nickel-based catalyst and a preparation method and application thereof: the catalyst is a supported catalyst which takes metal Ni as an active component and takes Zr-doped mesoporous molecular sieve Zr-SBA-16 as a carrier, can deeply remove CO in hydrogen-rich reformed gas to be less than 10ppm at the temperature of 180-230 ℃, and simultaneously, the selectivity of the methanation reaction of CO is higher than 50%. CN107376925B provides a low-temperature high-activity carbon dioxide methanation catalyst and a preparation method thereof, which adopts CO (NH)2)2Replace NaOH and Na2CO, providing the OH-and CO required for precipitation by slow hydrolysis at 90-120 ℃2Formation of homogeneous [ Ni1-x2+ Alx3+ (OH)2]x + (CO3) x/22-precipitation; the methanation catalyst starts to activate at about 150-250 ℃, and CO of more than 90 percent is obtained at 260-400 DEG C2Conversion and close to 100% CH4Selectivity and good hydrothermal stability. CN104511314A discloses a low temperature methanation catalyst, which comprises: the Raney alloy comprises an organic polymer material carrier and Raney alloy particles loaded on the surface of the organic polymer material carrier, wherein the Raney alloy contains 30-60 wt% of nickel, 0.01-5 wt% of iron, 0.01-5 wt% of chromium, 0.01-5 wt% of lanthanum and 30-60 wt% of aluminum; the catalyst has the advantages of high activity in low-temperature methanation reaction and the like. CN103706373A publicA low-temperature high-activity methanation catalyst and a preparation method thereof are provided; the catalyst takes metallic nickel as an active component, Al2O3Is a carrier, MgO is a structural assistant, and a proper amount of lanthanum oxide and manganese oxide are added as active assistants; the main components of the material by mass percent are respectively: 18 to 45 percent of NiO and 40 to 70 percent of Al2O3、5％～30％MgO、0.4％～5％La2O3、0.1％～5％MnO2The catalyst has the advantages of large specific surface area, uniform nickel dispersibility, good thermal stability, strong oxidation resistance, low active temperature, low adaptation to low hydrogen-carbon ratio and the like. CN109529840A discloses a CO2The catalyst is prepared into an alumina carrier containing carbon nano tubes at first, and then an impregnation method is adopted to load active components and an auxiliary agent; the carrier is made of Al2O3And carbon nano tube, the active component is NiO, and the auxiliary agent is selected from La2O3、CeO2One or two of them; based on the total mass percent of the catalyst, Al2O3The content of (2) is 55-85 wt%, the content of CNTs is 1-20 wt%, the content of active component NiO is 10-25 wt%, and the content of auxiliary agent is 0-5 wt%; the catalyst of the invention has high strength and CO2The low-temperature methanation activity is good.
The methanation reaction mainly consists of the following three reactions:
CO methanation reaction:
Figure BDA0002744584320000021
ΔH298K＝-208.2KJ/mol
CO2methanation reaction:
Figure BDA0002744584320000022
ΔH298K＝-165.0KJ/mol
water gas shift reaction:
Figure BDA0002744584320000023
ΔH298K＝-41.0KJ/mol
the methanation reaction is a reaction with strong heat release and reduced volume, so that the heat generated by the reaction is transferred out in time and the pressure of the reaction is increased, which is beneficial to the forward progress of the methanation reaction.
The low-temperature methanation reaction is a mature technology and is applied to industrial production. However, the catalyst components and the preparation method are in the patent protection mechanism and are monopolized by the countries such as Denmark Britain and the like for a long time. The methanation catalyst produced in China and applied to industry has the problems of high reaction temperature, high energy consumption, high operation difficulty and the like, so that the catalyst which can keep high activity and long service life in a low-temperature environment needs to be invented to replace the high-temperature methanation catalyst.
Disclosure of Invention
The invention aims to provide a catalyst which takes Ni as an active component and takes carbon nano-tubes, diatomite and Al2O3The low-temperature methanation catalyst is a composite structure auxiliary agent, one or more of La, Ce, Mg, Ca, Cu, Mn and Zr are modification auxiliary agents, and the methanation catalyst is prepared by adopting a coprecipitation method2High conversion rate and good stability.
In order to achieve the aim, the invention provides a low-temperature methanation catalyst which is prepared from carbon nano tubes, diatomite and Al2O3The catalyst is a composite structure assistant, Ni is an active component, an alkaline earth metal element, a rare earth element and a transition metal element are modification assistants, at least one of polyethylene glycol, sodium dodecyl benzene sulfonate and cellulose derivatives is a dispersing agent, and the content of the active component is 30-75% by mass of the total catalyst, preferably 40-60% by mass of the total catalyst; the content of the composite structure auxiliary agent is 20-60%, and preferably 30-50%; the content of the modifying auxiliary agent is 0.5-15%, preferably 7-10%; the content of the dispersant is 0.1-5%, preferably 1.5-2.5%.
In the composite structure auxiliary agent, the content of the carbon nano tube is 0.1-20% by total mass of the catalyst, the content of the diatomite is 0.1-30% by total mass of the catalyst, and the content of the alumina is 10-50% by total mass of the catalyst.
In the modification auxiliary agent, the alkaline earth metal element is at least one of Mg and Ca, the rare earth element is at least one of La and Ce, and the transition metal element is at least one of Cu, Mn and Zr.
The cellulose derivative of the present invention is at least one of carboxymethyl cellulose, sodium carboxymethyl cellulose, and the like.
The carbon nano tube is at least one of a multi-wall carbon nano tube and a single-wall carbon nano tube.
The invention also provides a preparation method of the low-temperature methanation catalyst, which comprises the following preparation steps:
(1) pretreatment of the carbon nanotubes: carrying out reflux treatment on the carbon nano tube in mixed acid with a volume ratio of nitric acid to sulfuric acid of 1: 1-6 for 1-6 h, washing the carbon nano tube by using deionized water until the pH value is 6.5-7.5, and drying the carbon nano tube for later use;
(2) preparing a precipitation solution: preparing a solution with the concentration of the Ni element being 0.5-2 mol/L from soluble salt of the Ni element, adding soluble salt of the Al element, soluble salt of an auxiliary metal element, diatomite and a dispersing agent into the solution for dissolving, and adding the carbon nano tube pretreated in the step (1) into the solution to prepare a solution to be precipitated;
(3) preparation of a precipitating agent: adding alkali and/or alkali soluble salt into deionized water to prepare a precipitator with the concentration of 1-3 mol/L;
(4) neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50-90 ℃, adding a solution to be precipitated and a precipitant, mixing and precipitating, and in the precipitation process, controlling the feeding rate of the solution to be precipitated and the precipitant by equipment, and maintaining the pH value of a neutralization reaction solution to be 9-11;
(5) after precipitation of the precipitation liquid is finished, aging is carried out for 1-3 h at 50-90 ℃, after aging is finished, suction filtration and washing are carried out on the obtained precipitate, after washing is carried out until the pH value is 6-8, a filter cake is dried for 1-10 h at 80-150 ℃, and then the filter cake is placed into a muffle furnace to be roasted for 1-10 h at the temperature of 300-700 ℃.
In the step (2), the soluble salt of the Ni element is nickel nitrate or nickel acetate; the soluble salt of the Al element is one or two of aluminum nitrate and aluminum sulfate, and the soluble salt of the auxiliary metal element can be nitrate, hydrochloride or other soluble salts; the dispersant is at least one of polyethylene glycol, sodium dodecyl benzene sulfonate and cellulose derivatives.
In the step (3), the alkali soluble salt is at least one of sodium carbonate, sodium bicarbonate and ammonium bicarbonate, and the alkali is one or two of sodium hydroxide and potassium hydroxide.
Compared with the prior art, the invention has the following advantages:
(1) adopts carbon nano tube, diatomite and Al2O3The catalyst is a composite structure auxiliary agent, can well adjust the hydroxyl distribution, the acidity and the alkalinity and the specific surface area on the surface of the catalyst, stabilize the active component and improve the dispersibility of the active component. The diatomite has a unique microporous structure, large specific surface area, strong adsorption capacity and good thermal stability. Having sp2The carbon nano tube with the-C forming surface not only has good electron transfer performance, but also can effectively improve the electron transfer performance to CO and CO2The adsorption capacity of the carbon nano tube is transferred to Ni active sites attached to the inside and the outside of the carbon nano tube, thereby effectively improving CO and CO2The conversion of (a); meanwhile, the carbon nanotube has a pore cavity structure and high stability, and the strength of the catalyst can be effectively improved.
(2) Alkaline earth metal elements, rare earth elements and transition metal elements are added as modification aids, so that the electron cloud density of the active component Ni can be increased, and the CO and CO are promoted2The dissociation capability of the catalyst is improved, and the low-temperature hydrogenation activity of the catalyst is enhanced.
(3) The stable pH value of the neutralization environment is always maintained in the precipitation process in the preparation process of the catalyst, so that the stability of the coprecipitation reaction is ensured.
(4) The dispersing agent is added in the preparation process of the catalyst, which is beneficial to the dispersion of the active component Ni and improves the activity of the catalyst.
(5) The low-temperature methanation catalyst prepared by the impregnation method needs to be impregnated and roasted for multiple times, and has complex process and high cost; the catalyst of the invention has simple preparation method and low cost, and is more suitable for industrialized popularization and application.
Compared with the existing methanation catalyst, the low-temperature methanation catalyst has excellent low-temperature methanation activity, low energy consumption and CO2The hydrogenation conversion rate is high, and the method is particularly suitable for low-concentration CO and CO2Methanation reaction. The preparation method of the low-temperature methanation catalyst is simple and has an industrial application prospect.
Detailed Description
An evaluation device: a10 ml methanation high throughput evaluation device was used.
The analysis method comprises the following steps: measuring the content of corresponding metal in the catalyst on an A240FS atomic absorption spectrometer; the raw materials and the product composition are analyzed by an Agilent 7890B gas chromatograph.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
(1) Pretreatment of the carbon nanotubes: the carbon nano tube is firstly treated by refluxing in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:1 for 1.5h, then washed by deionized water until the pH value is 7, and dried for later use.
(2) Preparing a precipitation solution: 100g of nickel acetate is weighed to prepare a solution with Ni concentration of 0.5mol/L, and then 28g of aluminum nitrate, 0.5g of cerium nitrate, 0.9g of calcium nitrate, 0.5g of copper nitrate, 10g of diatomite, 0.05g of pretreated carbon nano tube and 0.1g of polyethylene glycol are added into the solution to be dissolved and dispersed to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and a precipitator, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 2h at 90 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and a filter cake is dried for 6h at 120 ℃ and then is put into a muffle furnace to be roasted for 4h at 400 ℃.
Comparative example 1
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:1 for 1.5h, washing with deionized water until the pH value is 7, and drying for later use.
(2) Preparing a precipitation solution: 100g of nickel acetate is weighed to prepare a solution with Ni concentration of 0.5mol/L, and then 28g of aluminum nitrate, 10g of diatomite, 0.05g of pretreated carbon nano tube and 0.1g of polyethylene glycol are added into the solution to be dissolved and dispersed to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) And (3) a neutralization reaction precipitation process: and (3) placing the beaker in a water bath kettle at the temperature of 50 ℃, and mixing and precipitating the precipitation solution and the precipitant in the beaker. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation solution is finished, aging is carried out for 2h at 90 ℃, the precipitate is filtered and washed for many times until the pH value is 7, the filter cake is dried for 6h at 120 ℃, and the filter cake is roasted for 4h at 400 ℃ in a muffle furnace.
Example 2
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:5 for 5 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: weighing 45g of nickel nitrate to prepare a solution with Ni concentration of 2mol/L, and then adding 80g of aluminum sulfate, 5g of lanthanum nitrate, 6g of magnesium nitrate, 4g of copper sulfate, 3g of manganese nitrate, 0.1g of diatomite, 5.5g of pretreated carbon nano tube and 0.5g of sodium carboxymethylcellulose into the solution to dissolve and disperse to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 0.5 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and a precipitator, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 3h at 55 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, the filter cake is dried for 10h at 80 ℃, and then the filter cake is put into a muffle furnace for roasting for 10h at 330 ℃.
Comparative example 2
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:5 for 5 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 45g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 2mol/L, and then 120g of aluminum sulfate, 5g of lanthanum nitrate, 6g of magnesium nitrate, 4g of copper sulfate, 3g of manganese nitrate and 0.5g of sodium carboxymethylcellulose are added into the solution to be dissolved and dispersed to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 0.5 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 3h at 55 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and after a filter cake is dried for 10h at 80 ℃, the filter cake is put into a muffle furnace to be roasted for 10h at 330 ℃.
Example 3
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 3 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 1.5mol/L, and then 100g of aluminum nitrate, 3g of cerium nitrate, 2g of copper nitrate, 2g of manganese nitrate, 2g of zirconium oxychloride, 3g of diatomite, 1g of pretreated carbon nano tube and 0.8g of sodium dodecyl benzene sulfonate are added into the solution to be dissolved and dispersed, so as to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: a certain amount of sodium carbonate is weighed and added into deionized water to prepare a precipitator with the concentration of 1.5 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation solution is finished, aging is carried out for 2h at 80 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and a filter cake is dried for 4h at 100 ℃ and then is put into a muffle furnace to be roasted for 4h at 400 ℃.
Comparative example 3
(1) Pretreatment of the carbon nano tube: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 3 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 1.5mol/L, and then 120g of aluminum nitrate, 3g of cerium nitrate, 2g of copper nitrate, 2g of manganese nitrate, 2g of zirconium oxychloride, 1g of pretreated carbon nano tube and 0.8g of sodium dodecyl benzene sulfonate are added into the solution to be dissolved and dispersed, so as to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: a certain amount of sodium carbonate is weighed and added into deionized water to prepare a precipitator with the concentration of 1.5 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation solution is finished, aging is carried out for 2h at 80 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and a filter cake is dried for 4h at 100 ℃ and then is put into a muffle furnace to be roasted for 4h at 400 ℃.
Example 4
(1) Pretreatment of the carbon nano tube: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:4 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 1mol/L, and then 60g of aluminum nitrate, 1.5g of lanthanum nitrate, 1.2g of magnesium nitrate, 1g of copper nitrate, 0.5g of manganese nitrate, 1g of zirconium oxychloride, 4g of diatomite, 2g of pretreated carbon nano tube and 0.7g of sodium dodecyl benzene sulfonate are added into the nickel nitrate solution to be dissolved and dispersed to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 3h at 70 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and after a filter cake is dried for 4h at 120 ℃, the filter cake is put into a muffle furnace to be roasted for 4h at 450 ℃.
Comparative example 4
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:4 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: weighing 79g of nickel nitrate to prepare a solution with Ni concentration of 1mol/L, and then adding 75g of aluminum nitrate, 1.5g of lanthanum nitrate, 1.2g of magnesium nitrate, 1g of copper nitrate, 0.5g of manganese nitrate, 1g of zirconium oxychloride, 4g of kieselguhr and 0.7g of sodium dodecyl benzene sulfonate into the nickel nitrate solution to dissolve and disperse to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of sodium carbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 3h at 70 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and after a filter cake is dried for 4h at 120 ℃, the filter cake is put into a muffle furnace to be roasted for 4h at 450 ℃.
Example 5
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 1mol/L, and then 42g of aluminum sulfate, 2g of lanthanum nitrate, 1.5g of calcium nitrate, 1.2g of copper nitrate, 1.2g of manganese nitrate, 1g of zirconium oxychloride, 4g of diatomite, 2g of pretreated carbon nanotube and 1.3g of polyethylene glycol are added into the nickel nitrate solution to be dissolved and dispersed, so as to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: a certain amount of sodium bicarbonate is weighed and added into deionized water to prepare a precipitator with the concentration of 0.5 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 2h at 90 ℃, the precipitate is filtered and washed for a plurality of times until the pH value is 7, and the filter cake is dried for 3h at 140 ℃ and then is put into a muffle furnace to be roasted for 4h at 400 ℃.
Comparative example 5
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 1mol/L, and then 42g of aluminum sulfate, 2g of lanthanum nitrate, 1.5g of calcium nitrate, 1.2g of copper nitrate, 1.2g of manganese nitrate, 1g of zirconium oxychloride, 4g of sodium silicate, 2g of pretreated carbon nano tube and 1.3g of polyethylene glycol are added into the nickel nitrate solution to be dissolved and dispersed, so as to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: a certain amount of sodium bicarbonate is weighed and added into deionized water to prepare a precipitator with the concentration of 0.5 mol/L.
(4) And (3) a neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 2h at 90 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and a filter cake is dried for 3h at 140 ℃ and then is put into a muffle furnace to be roasted for 4h at 400 ℃.
Example 6
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with Ni concentration of 0.5mol/L, and then 20g of aluminum nitrate, 1g of lanthanum nitrate, 1g of magnesium nitrate, 0.5g of manganese nitrate, 2g of diatomite, 1g of pretreated carbon nano tube and 0.4g of carboxymethyl cellulose are added into the nickel nitrate solution to be dissolved and dispersed, so as to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of ammonium bicarbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 2h at 85 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and the filter cake is dried for 2h at 150 ℃, and then is put into a muffle furnace to be roasted for 2h at 600 ℃.
Comparative example 6
(1) Pretreatment of the carbon nanotubes: and (2) refluxing the carbon nano tube in mixed acid with the volume ratio of nitric acid to sulfuric acid being 1:3 for 4 hours, washing with deionized water until the pH value is 6.5-7.5, and drying for later use.
(2) Preparing a precipitation solution: 79g of nickel nitrate is weighed to prepare a solution with the Ni concentration of 0.5mol/L, and then 20g of aluminum nitrate, 1g of lanthanum nitrate, 1g of magnesium nitrate, 0.5g of manganese nitrate, 2g of diatomite and 1g of pretreated carbon nano tube are added into the nickel nitrate solution to be dissolved and dispersed to prepare a solution to be precipitated.
(3) Preparation of a precipitating agent: weighing a certain amount of ammonium bicarbonate, and adding deionized water to prepare a precipitator with the concentration of 1 mol/L.
(4) Neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50 ℃, adding the liquid to be precipitated and the precipitant into the beaker, and mixing and precipitating. In the precipitation process, the feeding rate of the solution to be precipitated and the precipitating agent is controlled by equipment, and the pH value of the neutralization reaction solution is maintained at 9-11.
(5) After the precipitation of the precipitation liquid is finished, aging is carried out for 2h at 85 ℃, after the aging is finished, the precipitate is filtered and washed for many times until the pH value is 7, and the filter cake is dried for 2h at 150 ℃, and then is put into a muffle furnace to be roasted for 2h at 600 ℃.
TABLE 1 summary of catalyst Properties
Figure BDA0002744584320000111
Figure BDA0002744584320000121
Catalyst applied to methanation reaction performance in crude hydrogen
The crude hydrogen used in the test was obtained from a Dalian standard gas and its properties are shown in Table 2.
TABLE 2 crude Hydrogen feed composition
Hydrogen gas Methane CO CO2
Balance gas 4.7％ 5015ppm 103ppm
Performing performance evaluation on the catalyst by adopting a methanation micro-reaction fixed bed reactor with the volume of 10ml and the reaction pressure of 2MPa, and performing performance evaluation on the catalysts of examples 1-6 and comparative examples 1-6 respectively; before the catalyst is evaluated, the catalyst needs to be subjected to reduction activation treatment, the activation process conditions are shown in table 3, and the performance evaluation data of the catalyst is shown in table 4.
TABLE 3 catalyst reduction activation Process conditions
Reducing gas Reduction temperature Airspeed Reduction time
50％H2+50％N2 350℃ 5000h-1 10h
TABLE 4 evaluation data of catalyst methanation Performance
Figure BDA0002744584320000122
Figure BDA0002744584320000131
Note: conversion rate (content in raw material-content in product)/content in raw material
Compared with the comparative example 1, the comparative example 1 does not contain any auxiliary agent, the methanation effect is poor, and the CO conversion rate of the example 1 reaches 100%.
Compared with the comparative example 2, the comparative example 2 does not contain carbon nano tubes and diatomite, a composite structure auxiliary agent is not formed, the methanation effect is poor, the methanation effect of the example 2 is obviously better than that of the comparative example 2, but the active component Ni is low, and CO are contained2The removal is incomplete.
Example 3 in comparison to comparative example 3, comparative example 3 did not contain diatomaceous earth, did not form a composite structure aid, and had a CO conversion similar to that of example 3, but for CO2The conversion of (a) is significantly lower than in example 3.
Example 4 in comparison with comparative example 4, comparative example 4 did not contain carbon nanotubes and did not form a composite structure aid, and both catalysts had 100% CO conversion, but comparative example 4 did CO2The conversion of (3) was lower than in example 4.
Example 5 in comparison to comparative example 5, which did not add diatomaceous earth but instead used sodium silicate as the silicon source, both catalysts had 100% conversion of CO, but comparative example 5 was for CO2The conversion of (3) was lower than in example 5. It can be found that by addingThe diatomite is added to form the composite structure auxiliary agent, so that the methanation performance is more excellent.
Example 6 in comparison with comparative example 6, comparative example 6 with no dispersant added, both catalysts with composite structure promoter, comparative example 6 for CO2The conversion of (a) is slightly lower.
Table 5 example 4 evaluation test of catalyst Process conditions
Figure BDA0002744584320000132
Figure BDA0002744584320000141
The evaluation and analysis data show that the carbon nano tube, the diatomite and the Al are formed2O3Methanation catalyst as assistant of composite structure for CO and CO2The catalyst has high conversion rate, excellent low-temperature hydrogenation activity, high airspeed operation capability and high industrial popularization and application value.

Claims (10)

1. The low-temperature methanation catalyst is characterized by comprising carbon nano tubes, diatomite and Al2O3Is a composite structure auxiliary agent, Ni is an active component, alkaline earth metal elements, rare earth elements and transition metal elements are modification auxiliary agents, and at least one of polyethylene glycol, sodium dodecyl benzene sulfonate and cellulose derivatives is a dispersing agent; based on the total mass of the catalyst, the content of the active component is 30-75%, the content of the composite structure auxiliary agent is 20-60%, the content of the modification auxiliary agent is 0.5-15%, and the content of the dispersing agent is 0.1-5%.
2. The low-temperature methanation catalyst as claimed in claim 1, wherein the low-temperature methanation catalyst comprises, by mass, 40-60% of the active component, 30-50% of the composite structure auxiliary agent, 7-10% of the modification auxiliary agent, and 1.5-2.5% of the dispersant.
3. The low-temperature methanation catalyst according to claim 1, wherein the composite structure auxiliary agent comprises 0.1 to 20% of carbon nanotubes, 0.1 to 30% of diatomite and 10 to 50% of alumina by mass of the total catalyst.
4. The low-temperature methanation catalyst according to claim 1, wherein in the modification auxiliary agent, the alkaline earth metal element is at least one of Mg and Ca, the rare earth element is at least one of La and Ce, and the transition metal element is at least one of Cu, Mn and Zr.
5. The low temperature methanation catalyst of claim 1, wherein the cellulose-based derivative is at least one of carboxymethyl cellulose and sodium carboxymethyl cellulose.
6. The low-temperature methanation catalyst of claim 1, wherein the carbon nanotubes are at least one of multi-walled carbon nanotubes and single-walled carbon nanotubes.
7. A method for preparing a low-temperature methanation catalyst according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) pretreatment of the carbon nanotubes: refluxing the carbon nano tube in mixed acid with a volume ratio of nitric acid to sulfuric acid of 1: 1-6 for 1-6 h, washing with deionized water until the pH value is 6.5-7.5, and drying for later use;
(2) preparing a precipitation solution: preparing a solution with the concentration of the Ni element being 0.5-2 mol/L from soluble salt of the Ni element, adding soluble salt of the Al element, soluble salt of an auxiliary metal element, diatomite and a dispersing agent into the solution for dissolving, and adding the carbon nano tube pretreated in the step (1) into the solution to prepare a solution to be precipitated;
(3) preparation of a precipitating agent: adding alkali and/or alkali soluble salt into deionized water to prepare a precipitator with the concentration of 1-3 mol/L;
(4) neutralization reaction precipitation process: placing the beaker in a water bath kettle at the temperature of 50-90 ℃, adding a solution to be precipitated and a precipitant, mixing and precipitating, and maintaining the pH value of a neutralization reaction solution to be 9-11 by controlling the feeding rate of the solution to be precipitated and the precipitant in the precipitation process;
(5) after the precipitation of the precipitation solution is finished, aging is carried out for 1-3 h at 50-90 ℃, after the aging is finished, the obtained precipitate is filtered and washed until the pH value is 6-8, the filter cake is dried for 1-10 h at 80-150 ℃, and then is roasted for 1-10 h at the temperature of 300-700 ℃.
8. The preparation method of the low-temperature methanation catalyst according to claim 7, wherein in the step (2), the soluble salt of the Ni element is nickel nitrate or nickel acetate; the soluble salt of the Al element is at least one of aluminum nitrate and aluminum sulfate; the soluble salt of the auxiliary metal element is at least one of nitrate and hydrochloride thereof.
9. The preparation method of the low-temperature methanation catalyst according to claim 7, wherein in the step (2), the dispersant is at least one of polyethylene glycol, sodium dodecyl benzene sulfonate and cellulose derivatives.
10. The preparation method of the low-temperature methanation catalyst according to claim 7, characterized in that in the step (3), the alkali soluble salt is at least one of sodium carbonate, sodium bicarbonate and ammonium bicarbonate; the alkali is at least one of sodium hydroxide and potassium hydroxide.
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Publication number Priority date Publication date Assignee Title
CN103769106A (en) * 2014-02-20 2014-05-07 厦门大学 Nickel-based methanation catalyst promoted by in-situ grew carbon nano tube and preparation method for nickel-based methanation catalyst
CN106622256A (en) * 2016-11-11 2017-05-10 中国五环工程有限公司 Preparation method of high-concentration CO methanation catalyst
CN109529840A (en) * 2018-11-29 2019-03-29 西南化工研究设计院有限公司 A kind of CO2Catalyst for Low-Temperature Methanation, preparation and application
JP2020032331A (en) * 2018-08-28 2020-03-05 株式会社豊田中央研究所 Methanation catalyst, manufacturing method therefor, and manufacturing method of methane
CN111097534A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Methanation catalyst and preparation method thereof
CN111686746A (en) * 2020-06-12 2020-09-22 北京石油化工学院 Low-temperature methanation catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769106A (en) * 2014-02-20 2014-05-07 厦门大学 Nickel-based methanation catalyst promoted by in-situ grew carbon nano tube and preparation method for nickel-based methanation catalyst
CN106622256A (en) * 2016-11-11 2017-05-10 中国五环工程有限公司 Preparation method of high-concentration CO methanation catalyst
JP2020032331A (en) * 2018-08-28 2020-03-05 株式会社豊田中央研究所 Methanation catalyst, manufacturing method therefor, and manufacturing method of methane
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