CN102463118A - Sulfur-tolerant methanation catalyst and its preparation method - Google Patents
Sulfur-tolerant methanation catalyst and its preparation method Download PDFInfo
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- CN102463118A CN102463118A CN2010105324437A CN201010532443A CN102463118A CN 102463118 A CN102463118 A CN 102463118A CN 2010105324437 A CN2010105324437 A CN 2010105324437A CN 201010532443 A CN201010532443 A CN 201010532443A CN 102463118 A CN102463118 A CN 102463118A
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Abstract
The invention relates to a sulfur-tolerant methanation catalyst and its preparation method, and relates to a sulfur-tolerant methanation catalyst which can be used under a wide operation condition particularly at high temperature and its preparation method, and the sulfur-tolerant methanation catalyst contains a carrier and an active component loaded on the carrier. The carrier is selected from alumina, silica, zirconium dioxide, active carbon or molecular sieve, the active component comprises a molybdenum oxide taken as a main active component, a cobalt oxide taken as a first auxiliary agent; and a zirconium oxide, a cerium oxide or a lanthanum oxide, or a mixture composed of at least two above oxides which is taken as a second auxiliary agent. The invention also discloses the preparation method of the sulfur-tolerant methanation catalyst which is composed of a dipping step, a drying step and a calcining step.
Description
Technical field
The present invention relates to a kind of methanation catalyst and preparation method thereof, relate in particular to a kind of catalyst for methanation in presence of sulfur that wide operating condition particularly can at high temperature be used and preparation method thereof that is applicable to.
Background technology
Natural gas is as low-carbon (LC), efficient, safe clean energy resource, and the consumption proportion that accounts for the disposable energy is with increasing.The natural gas allowable exploitation is very limited, and the source of the gas crisis causes the rise of nationwide Gas Prices.Therefore, lot of domestic and international company and research and development institution utilize coal or heavy oil and other fossil feedstock to prepare natural gas, and China has also carried out the project of a lot of coal preparing natural gas.The simple process flow of coal preparing natural gas is: coal gasification makes synthesis gas (CO, H
2), carry out desulfurization and decarburization and Water gas shift/WGS then, obtain CH through methanation workshop section at last
4
Catalytic coal gasifaction is the coal gasifying process of a kind of efficiency height and environmental protection, and the synthesis gas that the steam coal gasification produces generally contains H
2, CO, CO
2, CH
4, H
2S and unreacted H
2O.Wherein, H
2/ CO mol ratio is 1.5-2.5, CH
4Content is about about 20%, H
2, CO wants further methanation to generate CH
4
Ni is catalyst based to have very high methanation activity, but Ni is very responsive to S, and the sulfide that is easy to be synthesized in the gas poisons.For Ni was catalyst based, it was fatal and lasting that S poisons, because Ni is very strong to the absorption of S, and the H of low concentration in absorption S and the reaction system
2S can reach balance.Therefore, S content should be lower than 0.1～0.01ppm (volume content) in the Ni catalyst requirement unstripped gas.Contain a large amount of sulphur in the synthesis gas that catalytic coal gasifaction produces, thereby before carrying out methanation reaction, carry out desulfurization purification process expensive and consuming time synthesis gas.In addition, the easy carbon distribution inactivation of Ni will carry out Water gas shift/WGS in advance and regulate H
2/ CO ratio is greater than 3.
Mo methylmethane catalyst has many good qualities, and like anti-sulphur, is difficult for carbon distribution, and has shift activity, and shortcoming is that methanation activity is not high.If Mo base sulfur resistant catalyst has enough methanation activity, it will have great commercial significance.If dust burdening is less, then can save gas cleanup step in the synthesis gas that catalytic coal gasifaction makes.Unreacted steam does not need condensation to remove yet, because the Mo catalyst has the Water gas shift/WGS activity, can a part of CO in the synthesis gas be transformed to H
2Synthesis gas need not cooling can directly feed the catalyst for methanation in presence of sulfur bed, the energy consumption of having avoided gas to lower the temperature and afterwards heat up and cause earlier like this, and saved desulfurizing and purifying workshop section, save the cost of investment of production process greatly and reduced energy consumption.
The CO methanation is the reaction of strong heat release, and too high temperature can make catalysqt deactivation, and reduces methane production, and this will reduce temperature through inner or outside heat exchange.For example, catalyst for methanation in presence of sulfur can carry out the multistage filling, controls temperature through heat exchange between the bed, and produces high-grade steam simultaneously.Another kind method is to adopt fluidized-bed process, and fluid bed can be accelerated the heat transmission, prevents hot-spot.
It is active high that desirable methanation catalyst is not only wanted, and the life-span is long, and hear resistance will be got well.Can not cause that bed temperature sharply increases because the methanation reaction liberated heat is in time led away, cause the sintering of catalyst inactivation easily.
Generally speaking, traditional Mo base catalyst for methanation in presence of sulfur initial reaction temperature is 350 ℃, and the optimum response warm area is 450-550 ℃, and reaction pressure is 1.5-2.2MPa.In addition, the methane selectively of catalyst is lower, the highest 70-80% that is merely.
The method that improves catalyst activity and high-temperature stability has a lot, such as adding auxiliary agent or improving catalyst carrier.Zr, La, Ce or other rare-earth oxide usually use as carrier and auxiliary agent; For example; A kind of catalyst for methanation in presence of sulfur that is used for by preparing methane by synthetic gas is disclosed among patent CN1033580A1 and the CN85109423; Its main active component is vanadium, molybdenum or tungsten, and promoter is nickel and/or cobalt, and carrier is porous C eO
2Or ZrO
2, but do not provide the existence of each active component in this patent, the existence that does not yet have detailed preparation embodiment can infer each active component.Though this catalyst is at 500 ℃ of CO conversion ratios that can reach 80-88% down, its methane selectively is merely 30-50%, and is obviously on the low side.Another shortcoming of this catalyst is CeO
2Very big as the carrier consumption, this is unfavorable for reducing the catalyst cost, and CeO
2The specific area and the pore volume of carrier are all very little, thereby synthetic specific surface area of catalyst and pore volume are all less.Catalyst is after 20h is aging, and active and selectivity has obvious reduction, explains that catalyst stability is relatively poor.
Patent US4540714 is disclosed in the V base catalyst for methanation in presence of sulfur and adds auxiliary agent CeO
2Help improving catalyst performance.Patent US4491639 mentions that Zr, Ce etc. add in the sulfide catalyst of V, Mo or W, can strengthen the stability of catalyst, and this patent spells out does not use porous mass as carrier; But the sulfide of directly using above-mentioned metal is as catalyst, but do not mention the use of La in this patent, and the CO conversion ratio that is obtained in this patent is still lower; Under 530 ℃, be merely 50-78%; And the methane ratio from its product gas, its methane selectively is not high, is merely 70-80%.
Patent CN101745401 and CN101733115 also disclose catalyst for methanation in presence of sulfur; Wherein carrier is porous masses such as aluminium oxide or silica; Main reactive metal is one or more among Mo, W and the V in the active component; Second metal is one or more among Fe, Co, Ni, Cr, Mn, La, Y or the Ce, and the various metals in its active component all exist with the form of metal carbides.
Summary of the invention
First aspect; The invention provides a kind of catalyst for methanation in presence of sulfur; It comprises carrier and loads on the active component on this carrier, and wherein said carrier is selected from alundum (Al, silica, zirconium dioxide, active carbon or molecular sieve, and said active component comprises:
The oxide of molybdenum is as main active component;
The oxide of cobalt is as first auxiliary agent;
The oxide of the oxide of zirconium, the oxide of cerium, lanthanum or at least two kinds mixture in them are as second auxiliary agent.
Second aspect the invention provides a kind of preparation method of catalyst for methanation in presence of sulfur, and it comprises following sequential steps:
A prepares dipping solution, and said solution contains:
Molybdenum precursor and cobalt precursors; And,
At least a in zirconium precursors, cerium precursor or the lanthanum precursor;
B. use this dipping solution impregnated carrier;
C. the product to step b carries out drying;
D. the product of step c is calcined.
The third aspect, the present invention also provides the preparation method of another kind of catalyst for methanation in presence of sulfur, may further comprise the steps:
A. with the dipping solution impregnated carrier that comprises the molybdenum precursor, carry out drying and calcining then;
B. with the dipping solution impregnated carrier that comprises cobalt precursors, carry out drying and calcining then;
C. with comprising at least a dipping solution impregnated carrier in zirconium precursors, cerium precursor or the lanthanum precursor, carry out drying and calcining then;
Wherein the order of step a-c is not limit, and the carrier among the step a-c is an identical carrier.
Fourth aspect, the present invention also provides the catalyst for methanation in presence of sulfur that makes first aspect of the present invention to be contained H
2Product after the gas temperature programming vulcanizing treatment of S.
Detailed Description Of The Invention
In the first aspect of the present invention; Said catalyst for methanation in presence of sulfur comprises carrier and loads on the active component on this carrier; Wherein said carrier is selected from alundum (Al, silica, zirconium dioxide, active carbon or molecular sieve; These carriers are porous mass, and which kind of carrier those skilled in the art can select specifically to use according to the character of desired finished catalyst and according to their indexs such as specific area, surface acidity, pore volume, particle diameter and breaking strength, repeat no more at this.
In the said active component, the oxide of molybdenum is as main active component; The oxide of cobalt is as first auxiliary agent; And the oxide of the oxide of the oxide of zirconium, cerium, lanthanum or in them at least two kinds mixture as second auxiliary agent.Among the present invention, the oxide of the oxide of the oxide of said molybdenum, the oxide of cobalt, zirconium, the oxide of cerium or lanthanum refers to oxide or the hopcalite of various valence states of the various valence states of each metal respectively.For example, the oxide of molybdenum can be molybdenum trioxide, molybdenum dioxide or their mixture etc., and the oxide of cobalt can be cobalt protoxide, cobalt sesquioxide or their mixture, by that analogy.
The amount of active component is following: with the catalyst gross mass is benchmark, with MoO
3The oxide of molybdenum of meter accounts for 2%-20%, accounts for 0.5-10% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.2%-5%.In preferred embodiments, be benchmark with the catalyst gross mass, with MoO
3The oxide of molybdenum of meter accounts for 4%-15%, accounts for 1-5% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.4%-3%.This paper alleged with MoO
3Meter is meant that the quality with the oxide of various molybdenums all is converted to MoO
3Quality, then with the conversion after MoO
3Gross mass is represented the total quality of the oxide of molybdenums all in the catalyst.This conversion is well known to a person skilled in the art.
Second aspect of the present invention is the preparation method of the said catalyst for methanation in presence of sulfur of first aspect of the present invention, summarizes, and comprises common impregnation steps, drying steps and calcining step.Specifically, step a is the preparation dipping solution, and this solution contains molybdenum precursor and cobalt precursors, and comprises at least a in zirconium precursors, cerium precursor or the lanthanum precursor.Because this solution is used for impregnated carrier, so be referred to as dipping solution.Wherein, solvent is a water, and said molybdenum precursor is water-soluble molybdate, and said cobalt precursors is a water soluble cobaltous salt, and said zirconium precursors is water-soluble zirconates or water-soluble zirconates or zirconate, and said cerium precursor is water-soluble cerium salt, and said lanthanum precursor is water-soluble lanthanum salt.
Wherein said water-soluble molybdate is selected from sodium molybdate, potassium molybdate or ammonium molybdate, not hoping to introduce under the situation of foreign metal ion, preferably uses ammonium molybdate.
Said water soluble cobaltous salt can be selected from the cobalt salt of inorganic acid, and for example cobalt chloride, cobalt nitrate or cobaltous sulfate etc., or organic acid cobalt salt like cobalt acetate, cobalt oxalate etc., preferably use the cobalt salt of inorganic acid; Perhaps said water soluble cobaltous salt can be selected from the inferior cobalt salt of inorganic acid, and the for example inferior cobalt of cobalt chloride, colbaltous nitrate or sulfuric acid etc., or the inferior cobalt salt of organic acid like the inferior cobalt of acetate, the inferior cobalt of oxalic acid etc., preferably uses the inferior cobalt salt of inorganic acid.
Said water-soluble zirconates can selected among zirconium various inorganic acid salts or acylate, ZrCl for example
4, Zr (SO
4)
2, ZrOSO
4Deng, perhaps can selected among zirconium hydrochlorate or zirconic acid Ester, as long as its water soluble.
Said water-soluble cerium salt can be selected from the salt of various acid of the cerium of various valence states, and as long as the for example sulfate of cerium, nitrate, acetate or the like are its water soluble.
Said water-soluble lanthanum salt can be selected from the salt of various acid of the lanthanum of various valence states, and as long as the for example sulfate of lanthanum, nitrate, acetate or the like are its water soluble.
The concentration of each precursor in dipping solution can be calculated according to target content and the dipping efficient of active component in catalyst, and these are well known to a person skilled in the art.
In a preferred embodiment of the invention, before with the dipping solution impregnated carrier, can regulate the pH value of said dipping solution, so that each precursor more stably exists in solution.The step of target pH value and such adjust pH all is those skilled in the art's a conventional knowledge.For example, target pH value can scope can be 8-11.
In another preferred embodiment of the present invention, also comprise the complexing stabilizing agent in the said dipping solution, this complexing stabilizing agent is selected from hydramine, tartaric acid, ethylenediamine, one or more in urea or the ammoniacal liquor.The amount of complexing stabilizing agent accounts for the 1.0-1.5% of carrier quality.
In the second aspect of the present invention, step b is with said dipping solution impregnated carrier.Dipping method is well known to a person skilled in the art.Behind dipping, various active components are dispersed in the carrier hole.In a preferred embodiment of the invention, adopt equi-volume impregnating, the volume of promptly controlling dipping solution approximates the saturated adsorption volume of carrier.The benefit of doing like this is to make active component be dispersed on the carrier quantitatively.
In the second aspect of the present invention, step c is that the product to step b carries out drying.Can adopt any suitable drying means, for example, dry or dry or the two combination.In one embodiment, the product with step b dries under environmental condition.In another embodiment, with the oven dry of the product of step b, for example carried out preferred 8-12 hour 6-14 hour at 90-140 ℃, preferred 100-120 ℃ of following drying.In preferred embodiments, the product with step b dries earlier, and then oven dry under these conditions.
In second aspect of the present invention, steps d is that the product of step c is calcined.Calcining was carried out under 300-600 ℃ 2-10 hour under the condition that has oxygen to exist.Do not receive the restriction of any theory, think such calcining meeting with the precursors decompose of various active components and/or be oxidized to metal oxide, the metal oxide here is meant oxide or the hopcalite of various valence states of the various valence states of each metal.These metal oxides still are dispersed on the surfaces externally and internally of carrier and/or in the hole.
The third aspect of the invention is the another kind of preparation method of the said catalyst for methanation in presence of sulfur of first aspect of the present invention, summarizes, and comprises carrying out repeatedly with next group step: impregnation steps-drying steps-calcining step.Specifically,
A. with the dipping solution impregnated carrier that comprises the molybdenum precursor, carry out drying and calcining then;
B. with the dipping solution impregnated carrier that comprises cobalt precursors, carry out drying and calcining then;
C. with comprising at least a dipping solution impregnated carrier in zirconium precursors, cerium precursor or the lanthanum precursor, carry out drying and calcining then;
Wherein the order of step a-c is not limit, and the carrier among the step a-c is an identical carrier.
Wherein each dipping solution all only contains a kind of precursor of active component, and each dipping solution also can preferably be conditioned the pH value, and also can preferably contain the complexing stabilizing agent.Each precursor, complexing selection of stabilizers are as second aspect of the present invention.The condition of drying and calcining repeats no more also as second aspect of the present invention.
Fourth aspect of the present invention then provides the catalyst for methanation in presence of sulfur of first aspect of the present invention to be contained H
2Product after the gas temperature programming vulcanizing treatment of S.The wherein said H that contains
2The gas of S is H
2And H
2The mist of S.Wherein said temperature programming sulfuration is meant according to time dependent temperature carries out vulcanizing treatment to product.In one embodiment, said temperature programming vulcanizing treatment process is following: after being loaded into the catalyst of first aspect of the present invention in the reaction tube, feeding and contain 5 volume %H
2The H of S
2With H
2The S gaseous mixture.With the heating rate of 10 ℃/min the temperature of catalyst is heated to 400 ℃ from room temperature,, slowly is cooled to reaction temperature again at 400 ℃ of constant temperature sulfuration 4h.Do not receive any one theory, think after such temperature programming sulfidation is accomplished, have the sulfide that at least a portion, the preferred overwhelming majority change into the various valence states of each metal in the oxide of the various valence states of each metal.Carrier then has basically no variation.After the catalyst process temperature programming vulcanizing treatment of first aspect of the present invention, can be used for the methanation reaction of catalysis synthesis gas.
Embodiment
Through embodiment the present invention is detailed below, the embodiment that provides has been merely elaboration the present invention, and limits scope of the present invention never in any form.For example, although the carrier that uses in following examples is alundum (Al, in fact other listed carrier of this paper can use too.
Embodiment 1
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.06gCe (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3(this Al
2O
3Be γ-Al
2O
3, its physical property is following: specific area>=200m2/g, pore volume>=0.40mL/g, water absorption rate>=52%; Apparent density is 0.65-0.72g/mL, breaking strength>=80N/ grain, and particle diameter is 3-5mm; Drop in the mixed impregnant liquor for preparing down together), placement is spent the night, and dries naturally; Dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-a catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 2
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.26g ZrOCl
28H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100gAl
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoZr-a catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 3
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.07g La (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoLa catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 4
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last then.Flood 9.67g Co (NO then successively
3)
26H
2O, 5.06g Ce (NO
3)
36H
2The salting liquid of O preparation, per step dipping is dry 8h under 120 ℃ all, calcines 3h down at 450 ℃ at last, obtains the Mo-Co-Ce catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 5
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last then.Flood 9.67g Co (NO then successively
3)
26H
2O, 5.26g ZrOCl
28H
2The salting liquid of O preparation, per step dipping is dry 8h under 120 ℃ all, calcines 3h down at 450 ℃ at last, obtains the Mo-Co-Zr catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 6
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-b catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 7
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O, 6.45g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-c catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 1
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last and obtains the Mo catalyst then.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 2
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCo catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 3
Take by weighing 5.06g Ce (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Ce maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last and obtains the Ce catalyst then.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 4
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCe catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Activity rating:
Adopt fixed bed reactors to estimate the activity of the catalyst for methanation in presence of sulfur in each embodiment and the comparative example.The loadings of catalyst for methanation in presence of sulfur is 5mL, at first makes the catalyst of each embodiment preparation carry out the temperature programming sulfuration under the same conditions, begins to feed synthesis gas then and carries out the synthesis gas methanation reaction.Reaction condition is: reaction pressure (absolute pressure, down together) is 3.5MPa, and 500 ℃ of reaction temperatures, gas space velocity are 800h
-1, synthesis gas (percent by volume) CO/H
2Ratio is 2, with CO conversion ratio and CH
4Selectivity is represented catalyst activity and selectivity.
Hear resistance is estimated:
In order to estimate the hear resistance of catalyst of the present invention, also carried out following experiment.To pass through each catalyst behind the above-mentioned active appraisal experiment under reaction atmosphere behind 700 ℃ of following heat treatment 12h, estimate activity according to above-mentioned active appraisal experiment program again, but condition changes slightly, see Table 1 table and annotate.Observe CO conversion ratio and CH
4Whether selectivity has remarkable decline.If remarkable decline is arranged, explain that this catalyst is heat labile.
Table 1 has been listed with aforementioned various catalyst, through H
2/ H
2After S gaseous mixture temperature programming presulfurization is handled, the active testing result before heat-resisting and behind 700 ℃ of heat-resisting 12h respectively.
The various activity of such catalysts evaluation result of table 1 *
* appreciation condition: loaded catalyst: 5.0mL, temperature: 500 ℃, pressure: 3.5Mpa, air speed: 1000h
-1, H in the unstripped gas
2/ CO is 2.
The heat-resisting back of *: catalyst is reduced to 500 ℃ of results that survey behind 700 ℃ of reaction 12h behind 500 ℃ of active testings.
Interpretation of result: the catalyst in the embodiments of the invention has all been realized high relatively CO conversion ratio and CH
4Selectivity.And after 700 ℃ of following heat treatments, find the CO conversion ratio and the CH of the catalyst in the embodiments of the invention
4Selectivity only has a spot of decline, explains that catalyst tolerates of the present invention is hot good.By contrast, the catalyst of comparative example then shows CO conversion ratio and CH
4Optionally significantly descend, explain that they are thermo-labile.
Advantage of the present invention is following:
The invention provides a kind of catalyst for methanation in presence of sulfur, this catalyst is not only high to the selectivity of methane, and maximum characteristics are good heat resistances, can be 500 ℃ of following stable operations.It is worthy of note that catalyst of the present invention still can keep active preferably after experience under 700 ℃ the high temperature reaches 12 hours.In a word, this catalyst has the low temperature active height, the advantage that high-temperature stability is good.
Claims (13)
1. catalyst for methanation in presence of sulfur, it comprises carrier and loads on the active component on this carrier, and wherein said carrier is selected from alundum (Al, silica, zirconium dioxide, active carbon or molecular sieve, and said active component comprises:
The oxide of molybdenum is as main active component;
The oxide of cobalt is as first auxiliary agent;
The oxide of the oxide of zirconium, the oxide of cerium or lanthanum, or at least two kinds mixture in them are as second auxiliary agent.
2. the catalyst for methanation in presence of sulfur of claim 1, the oxide of the oxide of the oxide of wherein said molybdenum, the oxide of cobalt, zirconium, the oxide of cerium or lanthanum refer to oxide or the hopcalite of various valence states of the various valence states of each metal respectively.
3. the catalyst for methanation in presence of sulfur of claim 1 is a benchmark with the catalyst gross mass wherein, with MoO
3The oxide of molybdenum of meter accounts for 2%-20%, accounts for 0.5%-10% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.2%-5%.
4. the catalyst for methanation in presence of sulfur of claim 1 is a benchmark with the catalyst gross mass wherein, with MoO
3The oxide of molybdenum of meter accounts for 4%-15%, accounts for 1%-5% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.4%-3%.
5. the preparation method of a catalyst for methanation in presence of sulfur, it comprises following sequential steps:
A. prepare dipping solution, said dipping solution contains:
Molybdenum precursor and cobalt precursors; And,
At least a in zirconium precursors, cerium precursor or the lanthanum precursor;
B. use the dipping solution impregnated carrier of step a;
C. the product to step b carries out drying;
D. the product of step c is calcined.
6. the preparation method of a catalyst for methanation in presence of sulfur may further comprise the steps:
A. with the dipping solution impregnated carrier that comprises the molybdenum precursor, carry out drying and calcining then;
B. with the dipping solution impregnated carrier that comprises cobalt precursors, carry out drying and calcining then;
C. with comprising at least a dipping solution impregnated carrier in zirconium precursors, cerium precursor or the lanthanum precursor, carry out drying and calcining then;
Wherein the order of step a-c is not limit, and the carrier among the step a-c is an identical carrier.
7. claim 5 or 6 method; Wherein said molybdenum precursor is water-soluble molybdate, and said cobalt precursors is a water soluble cobaltous salt, and said zirconium precursors is water-soluble zirconates or water-soluble zirconates or zirconate; Said cerium precursor is water-soluble cerium salt, and said lanthanum precursor is water-soluble lanthanum salt.
8. claim 5 or 6 method also comprise the complexing stabilizing agent in the wherein said dipping solution, and this complexing stabilizing agent is selected from hydramine, tartaric acid, ethylenediamine, one or more in urea or the ammoniacal liquor.
9. the method for claim 8, wherein the quality of complexing stabilizing agent accounts for the 1.0-1.5% of the gross mass of said carrier.
10. claim 5 or 6 method, wherein said drying was carried out under 90-140 ℃ 6-14 hour, and said calcining was carried out under 300-600 ℃ 2-10 hour in the presence of oxygen.
11. the method for claim 5 or 6, wherein said dipping solution were conditioned the pH value before being used for impregnated carrier.
12. each catalyst for methanation in presence of sulfur is contained H among the claim 1-4
2Product after the gas temperature programming vulcanizing treatment of S.
13. the product of claim 12, the wherein said H that contains
2The gas of S is H
2And H
2The mist of S.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046474A (en) * | 1990-05-03 | 1990-10-31 | 湖北省化学研究所 | The vulcanization process of cobalt-molybdenum sulfur-resistant CO low change catalyzer |
| CN1235872A (en) * | 1998-05-20 | 1999-11-24 | 华南平 | Sulphur resistant carbon monoxide transfer catalyst |
| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
| CN101745401A (en) * | 2009-12-07 | 2010-06-23 | 中国科学院山西煤炭化学研究所 | Load type sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN101757941A (en) * | 2009-12-30 | 2010-06-30 | 山东齐鲁科力化工研究院有限公司 | Novel Co-Mo sulfur-tolerant shift catalyst and preparation method thereof |
-
2010
- 2010-11-02 CN CN2010105324437A patent/CN102463118A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046474A (en) * | 1990-05-03 | 1990-10-31 | 湖北省化学研究所 | The vulcanization process of cobalt-molybdenum sulfur-resistant CO low change catalyzer |
| CN1235872A (en) * | 1998-05-20 | 1999-11-24 | 华南平 | Sulphur resistant carbon monoxide transfer catalyst |
| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
| CN101745401A (en) * | 2009-12-07 | 2010-06-23 | 中国科学院山西煤炭化学研究所 | Load type sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN101757941A (en) * | 2009-12-30 | 2010-06-30 | 山东齐鲁科力化工研究院有限公司 | Novel Co-Mo sulfur-tolerant shift catalyst and preparation method thereof |
Cited By (18)
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