CN105435860A - Catalyst with non-uniformly-distributed cocatalyst and preparation method thereof - Google Patents
Catalyst with non-uniformly-distributed cocatalyst and preparation method thereof Download PDFInfo
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- CN105435860A CN105435860A CN201410397850.XA CN201410397850A CN105435860A CN 105435860 A CN105435860 A CN 105435860A CN 201410397850 A CN201410397850 A CN 201410397850A CN 105435860 A CN105435860 A CN 105435860A
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Abstract
The present invention discloses a catalyst with a non-uniformly-distributed cocatalyst component, the catalyst comprises a carrier and a main catalyst supported on the carrier, the carrier comprises a crystal nucleus, a carrier matrix material and the cocatalyst; the concentration distribution of the cocatalyst in the catalyst is non-uniform, and the distribution of the cocatalyst is progressive increase type or progressive decrease type. The present invention also discloses a preparation method of the catalyst, and the preparation method is as follows: in the presence of the crystal nucleus, water, the carrier matrix material, a binder and a saturated solution containing the cocatalyst are continuously mixed by a rolling ball method, the rate of addition of the saturated solution containing the cocatalyst is controlled to obtain a carrier precursor; first drying and calcining of the carrier precursor are sequentially performed to obtain the carrier; and the obtained carrier is contacted with a solution containing the main catalyst, and second drying and thermal decomposition are performed. The catalyst has excellent methanation catalytic activity and hydrogen purifying effect.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of co-catalyst non-uniform Distribution.
Background technology
Co-catalyst is a small amount of material be added in catalyst, it is the auxiliary element of catalyst, itself do not have activity or activity very little, but it is added to after in catalyst, the chemical composition of catalyst, chemical constitution, ionic valence condition, Acidity of Aikalinity, lattice structure, surface structure, pore structure, dispersity and mechanical strength etc. can be changed, thus improve the activity of catalyst, selective, stability and life-span.Such as co-catalyst can promote the heat endurance of carrier, slows down the coking of active component, reduces acidity, interval active component and minimizing sintering etc., and co-catalyst itself often has the function of certain active component.Effect of co-catalyst is often very large, and same major catalyst adds different co-catalysts, and its effect is different, and co-catalyst containing graded effect often than many containing graded effect sensitivity of carrier.Co-catalyst can add with elementary state, also can add with combined form.Sometimes add one, sometimes then add multiple.Reciprocation can be there is, so the effect of co-catalyst is more complicated between several co-catalyst.The selection of co-catalyst and research are problems very important in catalytic field.
Co-catalyst is divided into structural type and electron type two class by the unusual of the mechanism of action.The effect of structural type co-catalyst mainly improves dispersiveness and the heat endurance of active component.By adding this co-catalyst, make the small grains of active component spaced apart, not easy-sintering; Also can generate dystectic compound or solid solution with active component and reach thermally-stabilised, also can improve activity.Electron type co-catalyst, its effect changes the electronic structure of major catalyst, promotes catalytic activity and selective.Research shows, catalytic activity and its surface electronic of metal ability of giving and accepting is relevant, has the metal of vacant bonding orbital, have strong attraction, and the power of adsorption capacity is closely connected to electronics with catalytic activity.Such as in the iron catalyst of synthetic ammonia, because Fe is transition elements, free d track can receive electronics, therefore at Fe-Al
2o
3in add K
2after O, the latter plays electron donor effect, and electronics is passed to Fe, and the electron density of Fe atom is increased, and improves its activity, so K
2o is the co-catalyst of electron type.
Carrier, as the important component part of catalyst, is the dispersant of major catalyst, binder or supporter, is the skeleton of load major catalyst.The function of carrier mainly provides effective surface and suitable pore structure, strengthens the mechanical strength of catalyst, makes catalyst have the ability of certain adaptation external world change, improves the heat conductivity of catalyst and provide additional activated centre etc.The macrostructure of catalyst, as specific surface, pore structure, porosity and pore-size distribution etc., can have a great impact the activity and selectivity of catalyst, and this macrostructure is often decided by carrier.In order to adapt to industrially to put by force/needs of the endothermic reaction, carrier generally should have larger thermal capacitance and good thermal conductivity, reaction heat energy is made to pass out rapidly/enter, avoid hot-spot and cause the sintering of catalyst and inactivation or device damage, the side reaction under high temperature can also be avoided, thus improve the selective of catalyst.
Methanation reaction is mainly used in ethylene industry, synthetic ammonia, purified hydrogen and coal gasification field, is intended to CO to be converted into lighter hydrocarbons, or impurity CO in removing unstripped gas thus reach the object of purification.As the simplest F-T synthesis reaction, CO methanation has that calorific value is high, conversion ratio is high, product is single and the advantage such as good in economic efficiency.
The reaction equation of methanation is as follows:
CO+3H
2→CH
4+H
2OΔH
0＝-206KJ/mol
CO
2+4H
2→CH
4+2H
2OΔH
0＝-165KJ/mol
Domestic methanation catalyst is mainly J series, such as J103, J104, J105 etc.These catalyst are mainly active component with Ni, and belong to nickel system active component, nickel content is generally between 10-40wt%.Once there is inactivation in J105 catalyst, one of trace it to its cause, be catalyst deficient in stability, high temperature causes active component to be reunited in the process of application, and activated centre is reduced.Methanation catalyst in disclosed a lot of patent is also take nickel as major catalyst, adds other co-catalysts to improve the Activity and stabill of catalyst simultaneously.Co-catalyst disclosed in patent CN102527405A comprises lanthanum, cerium, manganese, lithium, vanadium.Disclosed in patent CN102513119A, catalyst components mass percent consists of: NiO20-40wt%, La
2o
310-20wt%, Al
2o
340-60wt%, graphite 3-10wt%.These above-mentioned catalyst, have good methanation activity in respective system, but do not study the distribution of concentration in catalyst granules of co-catalyst.
Specific to the catalyst of methanation reaction taking nickel as major catalyst, the content of the activity of catalyst and the size of nickel crystallite and nickel is closely related: nickel crystallite is less, and nickel degree of scatter is in the catalyst better, and the activity of catalyst is higher; The content of nickel is larger, and have more activated centres to be formed, the activity of catalyst is higher.The activity that co-catalyst obviously can change catalyst is added, such as alkali metal catalyst and rare earth co-catalyst in catalyst.The effect of alkali metal catalyst mainly changes the distribution of nickel crystallite, adding by alkali metal catalyst, and co-catalyst has a significant effect to the distribution of nickel on carrier and CO Hydrogenation.Rare earth co-catalyst not only significantly enhances decentralization and the methanation activity of nickel, and also directly affect the electronic state of surface nickel atoms, to different rare earth co-catalysts, these effects are different.Find the electronic state utilizing rare earth adjustment of cocatalyst surface nickel atoms, become the effective way improving methanation catalyst.Adding of rare earth co-catalyst crystal structure is changed simultaneously, thus make carrier surface modification, inhibit NiAl
2o
4the generation of spinelle, improves the decentralization of NiO, and rare earth co-catalyst itself exists with high degree of dispersion state.Rare earth co-catalyst makes the activity of nickel-base catalyst increase, not only there is the reason of its space structure aspect, and the electronic effect between them also plays an important role, it is basic anhydride that its electronic effect shows as rare earth on the one hand, decrease its electron-withdrawing power with surface acid center effect, nickel metal/d band electron deficient state is alleviated.
Summary of the invention
The object of the invention is, in order to overcome the problems referred to above, to provide a kind of applied range, to the catalyst of the good co-catalyst non-uniform Distribution of the catalytic activity of methanation reaction.
The present inventor finds: in catalyst, the distribution of active component (major catalyst and co-catalyst) directly affects the utilization rate of inner surface of catalyst granules.And thulium is as the preferred co-catalyst in catalyst of the present invention, not only can play the effect of dispersion size of nickel crystallite, and adding of thulium makes nickel crystallite diminish, the decentralization of nickel crystallite is uprised, effectively inhibit growing up of nickel crystallite, its reason is that the interaction of metal between the decentralization and carrier of carrier surface is closely related, the clinkering of nickel microcrystalline grain when high-temperature process can be suppressed to grow up simultaneously, slowed down the clinkering speed of nickel crystallite, causes the raising of metal dispersity.Therefore thulium directly has influence on the activity of catalyst in the distribution of catalyst external surface and duct ectonexine.Further, inventor finds that the manganese that adds in the catalyst and magnesium contribute to improving the stability of catalyst and suppresses major catalyst crystal to grow up reunion, molybdenum and tungsten contribute to the resistance to SO_2 and the activity that improve catalyst, add the dispersion that noble metal also contributes to major catalyst, reduce grain size, thus improve the activity of methanation reaction.
To achieve these goals, the invention provides a kind of catalyst of co-catalyst non-uniform Distribution, described catalyst comprises carrier and load major catalyst on this carrier, and described carrier comprises nucleus, carrier matrix material and co-catalyst; The CONCENTRATION DISTRIBUTION of described co-catalyst is heterogeneous in the catalyst, outer surface along described nucleus points to the direction of the outer surface of described catalyst, described co-catalyst be distributed as increment type or decrescendo, with the total amount of described catalyst for benchmark, the content of described major catalyst is 10-90wt%, and the content of described carrier is 10-90wt%.
Present invention also offers a kind of preparation method of catalyst of co-catalyst non-uniform Distribution, the method comprises the following steps: under the existence of nucleus, with rolling ball method, water, carrier matrix material, binding agent and co-catalyst saturated solution are mixed continuously, what control co-catalyst saturated solution adds speed, and the CONCENTRATION DISTRIBUTION obtaining wherein co-catalyst is the carrier predecessor of increment type and/or decrescendo; Described carrier predecessor is carried out the first oven dry successively and roasting obtains carrier; The carrier obtained is contacted with major catalyst solution, then carries out the second oven dry and thermal decomposition.
The Catalysts and its preparation method of co-catalyst non-uniform Distribution of the present invention, its Heterosis exists:
1, catalyst of the present invention can be applicable to different reaction types: different reaction types has different reaction velocities, temperature, the extent of reaction, has different rate-determining steps when reacting.Can according to reaction type preparation or the catalyst selecting cocatalyst component distribution this reaction the most applicable, the methanation activity of catalyst prepared by the inventive method is higher, and has the effect of purified hydrogen.
2, catalyst of the present invention has applicability widely, go for the field that great majority need to carry out methanation reaction, such as ethylene industry, synthetic ammonia, industries, fuel cell and coal gasification field, and higher catalytic activity is had under very wide in range reaction condition.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 represents the structural representation of catalyst of the present invention.
Description of reference numerals
0-nucleus, 1-internal layer, 2-skin
3-nucleus outer surface is to the distance of catalyst external surface
Detailed description of the invention
In the present invention, in case of no particular description, the internal layer of described catalyst and outer field thickness proportion are 1:1.
The invention provides a kind of catalyst of co-catalyst non-uniform Distribution, described catalyst comprises carrier and load major catalyst on this carrier, and described carrier comprises nucleus, carrier matrix material and co-catalyst; The CONCENTRATION DISTRIBUTION of described co-catalyst is heterogeneous in the catalyst, outer surface along described nucleus points to the direction of the outer surface of described catalyst, described co-catalyst be distributed as increment type or decrescendo, with the total amount of described catalyst for benchmark, the content of described major catalyst is 10-90wt%, and the content of described carrier is 10-90wt%.
According to the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, preferably, in the skin of described catalyst co-catalyst concentration ratio described in catalyst internal layer in the concentration height 0.2-12wt% of co-catalyst, more preferably high 1.5-7wt%.
According to the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, preferably, in the skin of described catalyst co-catalyst concentration ratio described in catalyst internal layer in the low 0.2-12wt% of concentration of co-catalyst, more preferably low 1.5-7wt%.
According to the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, what the CONCENTRATION DISTRIBUTION of described co-catalyst can meet the function of conventional increment type and other functions increases progressively interval.
According to one embodiment of the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, the CONCENTRATION DISTRIBUTION of described co-catalyst can meet with following formula 1,
C
help increasing=a × R
2+ b × R+c formula 1
Wherein, C
help increasingfor the concentration of co-catalyst, unit is wt%; The position of R corresponding to the concentration of corresponding co-catalyst is to the distance of nucleus outer surface, and unit is mm; A is zero or normal number, and b is constant, and c is zero or negative constant.Under preferable case, in the present invention, a is the arbitrary constant of 0-10; B and c is identical or different, is selected from the arbitrary constant of 0-20 independently of one another.
According to the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, the CONCENTRATION DISTRIBUTION of described co-catalyst can meet the conventional function of decrescendo and the interval of successively decreasing of other functions.
According to one embodiment of the present invention, when the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, the CONCENTRATION DISTRIBUTION of described co-catalyst can meet with following formula 2,
C
help and subtract=-d × R
2-e × R+f formula 2
Wherein, C
help and subtractfor the concentration of co-catalyst, unit is wt%; The position of R corresponding to the concentration of corresponding co-catalyst is to the distance of nucleus outer surface, and unit is mm; D is zero or normal number, and e is constant, and f is zero or negative constant.Under preferable case, in the present invention, d is the arbitrary constant of 0-10, e and f is identical or different, is selected from the arbitrary constant of 0-20 independently of one another.
According to the present invention, the distribution of the actual concentrations of co-catalyst described in described catalyst can by control in Kaolinite Preparation of Catalyst process containing cocatalyst saturated solution add speed to adjust.Particularly, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, the adding speed and can meet with the function shown in following formula 3 of the described saturated solution containing cocatalyst,
V
help increasing=g × t
2+ h × t+i formula 3
Wherein, v
help increasingadd speed for the described saturated solution containing cocatalyst, unit is g/min; T is the interpolation time of the saturated solution containing cocatalyst, and unit is min; G is zero or normal number, and h is constant, and i is zero or negative constant.Under preferable case, in the present invention, g is the arbitrary constant of 0 ﹤ g ﹤ 1, h and i is identical or different, is selected from the arbitrary constant of 0-1 independently of one another.
When the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, the adding speed and can meet with the function shown in following formula 4 of the described saturated solution containing cocatalyst,
V
help and subtract=-j × t
2-k × t+l formula 4
Wherein, v
help and subtractadd speed for the described saturated solution containing cocatalyst, unit is g/min; T is the interpolation time of the saturated solution containing cocatalyst, and unit is min; J is zero or normal number, and k is constant, and l is zero or negative constant.Under preferable case, in the present invention, j and l is identical or different, and wherein j is the arbitrary constant of 0 ﹤ j ﹤ 1, and l is the arbitrary constant of 0 ﹤ l ﹤ 1, and k is the arbitrary constant being selected from 0-1.
It will be appreciated by persons skilled in the art that in the present invention, described t constantly increases along with the growth of catalyst.
According to the present invention, with the total amount of described catalyst for benchmark, the content of described major catalyst is preferably 10-90wt%, is more preferably 20-80wt%.
According to the present invention, with the total amount of described catalyst for benchmark, the content of described carrier is preferably 10-90wt%, is more preferably 20-80wt%.
According to the present invention, the co-catalyst of the routine that described co-catalyst can be known to the skilled person, is preferably at least one in alkali metal, alkaline-earth metal, transition metal and rare earth metal; Preferably, described co-catalyst can be selected from least one in following metal: sodium, magnesium, barium, manganese, lanthanum, cerium, samarium, europium, gadolinium, erbium, thulium, molybdenum and yttrium.
In the present invention, described co-catalyst adds in a salt form, and preferably the saturated solution containing cocatalyst of the present invention can be at least one saturated solution in sodium nitrate, barium nitrate, lanthanum nitrate, lanthanum sulfate, lanthanum chloride, manganese nitrate, magnesium nitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, gadolinium nitrate and ammonium molybdate.
According to the present invention, the major catalyst of the routine that described major catalyst can be known to the skilled person, is preferably nickel.In the present invention, described major catalyst adds in a salt form, therefore, preferred the present invention, with at least one form in nickel acetate, nickel nitrate, nickel hydroxide, nickelous sulfate and nickelous carbonate, more preferably adds major catalyst with the form of at least one in nickel nitrate, nickelous sulfate and nickel acetate.
In the present invention, in case of no particular description, the percentage composition of described major catalyst and co catalysis is all with the pure element form calculus of non-salt.According to the present invention, with the total amount of described catalyst for benchmark, the content of described co-catalyst can be 0.1-20wt%, is preferably 0.5-15wt%.
According to the present invention, the carrier matrix material that described carrier matrix material and described nucleus can be known to the skilled person and nucleus, be preferably Al
2o
3, SiO
2, TiO
2, ZrO
2, MgO, CeO
2, sepiolite, kaolin, aluminous cement, silica gel, molecular sieve, zeolite, graphite, TiO
2-Al
2o
3, ZrO
2-Al
2o
3, ZrO
2-SiO
2in at least one.
According to the present invention, the binding agent of the routine that described binding agent can be known to the skilled person, is preferably at least one in nitric acid, ethanol, paraffin and starch, is more preferably starch adesive.
The invention provides a kind of preparation method of catalyst of co-catalyst non-uniform Distribution, the method comprises the following steps: under the existence of nucleus, with rolling ball method, water, carrier matrix material, binding agent and the saturated solution containing cocatalyst are mixed continuously, what control the saturated solution containing cocatalyst adds speed, and the CONCENTRATION DISTRIBUTION obtaining wherein co-catalyst is the carrier predecessor of increment type and/or decrescendo; Described carrier predecessor is carried out the first oven dry successively and roasting obtains carrier; The carrier obtained is contacted with the solution containing major catalyst, then carries out the second oven dry and thermal decomposition.
In described method provided by the invention, to the interpolation speed of described water, described carrier matrix material, described binding agent, there is no particular limitation, those skilled in the art can select as required in the various technological means that this area routine uses, as long as described water, described carrier matrix material, described binding agent and the described saturated solution containing cocatalyst can be made to mix continuously.To the method controlling described interpolation speed, there is no particular limitation, such as, pump, flowmeter and funnel can be adopted to control the interpolation speed of each raw material.
Under preferable case, in described method provided by the invention, be 100 parts by weight with total consumption of described nucleus and described carrier matrix material, the consumption of described water can be 10-60 weight portion, is preferably 30-40 weight portion.
In the present invention, preferred described nucleus is identical with the essence of described carrier matrix material, but both have difference on grain size, and generally speaking, the particle diameter of described nucleus is greater than the particle diameter of described carrier matrix material.Those skilled in the art can select as required in the scope that routine uses.
In described method provided by the invention, be 100 parts by weight with total consumption of described nucleus and described carrier matrix material, the consumption of described binding agent can be 20-50 weight portion, is preferably 25-35 weight portion.
In described method provided by the invention, be 100 parts by weight with total consumption of described nucleus and described carrier matrix material, the consumption of the described saturated solution containing cocatalyst can be 1-40 weight portion, is preferably 10-30 weight portion.
In described method provided by the invention, be 100 parts by weight with total consumption of described nucleus and described carrier matrix material, the weight ratio of the consumption of described nucleus and described carrier matrix material can be 1:50-300, is preferably 1:100-200.
In the present invention, the particle diameter of described nucleus can be 0.5-1.5mm, is preferably 0.8-1.2mm.
Before described method provided by the invention can also be included in and use nucleus and carrier matrix material, drying process is carried out to nucleus and carrier matrix material.The condition of described drying process can be implemented according to the condition of the drying process of this area routine and mode of operation.Baking temperature can be 100-150 DEG C, is preferably 120 DEG C; Drying time can be 2-5h, is preferably 3h.
In the present invention, described water, described carrier matrix material and described binding agent add with uniform speed substantially.Under preferable case, described water, described carrier matrix material and described binding agent, in 10-60min, preferably all add in 20-40min.In described method provided by the invention, described nucleus preferably added before the mixing of enforcement rolling ball method.
In the present invention, described rolling ball method refers to centered by nucleus, in bowling machine, add water, binding agent, carrier matrix material and the material such as saturated solution containing cocatalyst with the speed of constant speed or change, then constantly operated by bowling machine, make the method that catalyst is formed.
In the present invention, in described process water, carrier matrix material, binding agent and the saturated solution containing cocatalyst mixed continuously, the particle diameter of the described carrier predecessor of final gained can be 3-10mm, is preferably 4-6mm.
In the present invention, when in described carrier predecessor, the CONCENTRATION DISTRIBUTION of co-catalyst is increment type, described first dries and can implement according to the condition of the oven dry of this area routine and mode of operation, preferably, drying and warning speed is 30-60 DEG C/h, oven dry equilibrium temperature is 60-100 DEG C, and the time is 4-6h.In the present invention, in case of no particular description, described equilibrium temperature refer to drying and warning speed rise to a certain temperature and maintain temperature; Described drying time refers to the time maintaining equilibrium temperature and dry.
In the present invention, when in described carrier predecessor, the CONCENTRATION DISTRIBUTION of co-catalyst is decrescendo, described first dries and can implement according to the condition of the oven dry of this area routine and mode of operation, in order to form more stable catalyst of the present invention, preferably, drying and warning speed is 70-100 DEG C/h, and oven dry equilibrium temperature is 100-160 DEG C, and the time is 1-3h.
In the present invention, described roasting can be implemented according to the condition of the roasting of this area routine and mode of operation, and preferably, temperature is 200-1000 DEG C, is preferably 500-600 DEG C; Time is 2-8h, is preferably 2-5h.
In the present invention, described the process that the carrier obtained contacts with the solution containing major catalyst can be adopted the method that well known to a person skilled in the art and contacted with the solution containing major catalyst by carrier, preferably by described carrier and the described solution impregnation containing major catalyst, to time of described dipping, there is no particular limitation, and those skilled in the art can select according to conventional dip time.Preferably, the described solution containing major catalyst is saturated solution; The preferred dry method of described dipping, i.e. equi-volume impregnating.
In the present invention, described second dries and can implement according to the condition of the oven dry of this area routine and mode of operation, and preferably, drying rate of temperature fall is 30-80 DEG C/h, and oven dry equilibrium temperature is 40-160 DEG C, and the time is 1-6 hour; More preferably, drying rate of temperature fall is 30 DEG C/h, and drying equilibrium temperature is 40 DEG C, and the time is 2-6 hour.
In the present invention, described thermal decomposition can be implemented according to the condition of the thermal decomposition of this area routine and mode of operation, and preferably, temperature is 200-600 DEG C, and the time is 2-8 hour.
According to one of the present invention preferred embodiment, such as in the catalyst shown in Fig. 1,0 region representation nucleus, the internal layer of 1 region representation catalyst of the present invention, the skin of 2 region representation catalyst of the present invention, 3 represent that in catalyst of the present invention, nucleus outer surface is to the distance of catalyst external surface, and when utilizing rolling ball method to prepare catalyst of the present invention, the length of 3 can constantly increase.
It should be noted that, above-mentioned embodiment illustrates instead of restriction the present invention, and under the scope not departing from claims, those skilled in the art can design many optional embodiments.In addition, also can be combined between the concrete technical characteristic of each described in above-mentioned detailed description of the invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, the method detecting each content of material in the catalyst prepared is: the catalyst prepared first is used resin embedding, then solidifies and cuts into slices, being detected by the catalyst section ESEM obtained; In case of no particular description, the various reagent used in following examples are all from being purchased.
Embodiment 1
Get appropriate Al
2o
3nucleus and Al
2o
3powder (carrier matrix material, the lower with) baking oven that is placed in 120 DEG C respectively dry 3 hours, to remove surface moisture, for subsequent use.
Get the Al that 10g is dried
2o
3nucleus (particle diameter is about 1mm, standard No. HG/T3927-2007) adds in bowling machine, in bowling machine, then add the Al of oven dry with the constant speed of 41.7g/min simultaneously
2o
3powder, to add pure water with the constant speed of 12.5g/min, add starch adesive with the constant speed of 12.5g/min and add samaric nitrate saturated solution with the speed of change.Wherein, the speed that adds of samaric nitrate saturated solution meets increment type quadratic function v
samarium increases=-0.006+0.026t
2(v
samarium increasesadd speed for samaric nitrate saturated solution, unit is g/min; T is the interpolation time (lower same) of the saturated solution containing cocatalyst, and unit is min).The carrier predecessor that particle diameter is about 5mm is obtained through 30min.Adopt the mode of temperature programming to be warmed up to 80 DEG C with the speed of 45 DEG C/h the carrier predecessor of gained, and continue oven dry 5 hours at such a temperature.By the material roasting 4 hours at 600 DEG C after drying, after being cooled to room temperature, obtain carrier.
Getting 173.4g nickel nitrate (being the nickel nitrate containing 6 crystallizations water, lower same) is dissolved in 50g deionized water completely, then impregnated in the above-mentioned prepared carrier of 65g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopts the mode of programmed cooling to cool to equilibrium temperature 80 DEG C with the speed of 50 DEG C/h from 100 DEG C, and dry 3 hours under this equilibrium temperature.Be exposed in air by the material after drying, thermal decomposition 4 hours at 500 DEG C, obtaining co-catalyst along the radial direction of described catalyst granules be the catalyst prod that increment type distributes.After testing, in the catalyst prod of gained, the distribution of samarium meets functional equation: C
samarium increases=-0.194+0.774R
2; And the content of nickel element is 35wt%, the content of samarium element is 4wt%.
Embodiment 2
Get appropriate SiO
2nucleus and SiO
2powder be placed in respectively 120 DEG C baking oven dry 3 hours, to remove surface moisture, for subsequent use.
Get the SiO that 10g is dried
2nucleus (particle diameter is about 0.8mm or standard No. HG/T2765.3-2005) adds in bowling machine, in bowling machine, then add the SiO of oven dry with the constant speed of 31.25g/min simultaneously
2powder, adds pure water with the constant speed of 12.5g/min, adds starch adesive and add manganese nitrate saturated solution with the speed of change with the constant speed of 10g/min.Wherein, the speed that adds of manganese nitrate saturated solution meets increment type quadratic function v
manganese increases=-0.003+0.017t
2(v
manganese increasesspeed is added, g/min for manganese nitrate saturated solution), obtain through 40min the carrier predecessor that particle diameter is about 4mm.Adopt the mode of temperature programming to be warmed up to 100 DEG C with the speed of 40 DEG C/h the carrier predecessor of gained, and continue oven dry 4 hours at such a temperature.By the material roasting 6 hours at 400 DEG C after drying, after being cooled to room temperature, obtain carrier.
Getting 112g nickelous sulfate (containing six molecular crystalline water, lower same) is dissolved in 280g deionized water completely, then impregnated in the above-mentioned prepared carrier of 75g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopts the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, and keep oven dry 5 hours at such a temperature.Material after drying is exposed in air, thermal decomposition 6 hours at 300 DEG C, obtains the catalyst prod of co-catalyst increment type distribution.After testing, in the catalyst prod of gained, the distribution of manganese meets functional equation: C
manganese increases=-0.605+3.78R
2; And the content of nickel element is 25wt%, the content of manganese element is 10wt%.
Embodiment 3
Get appropriate TiO
2nucleus and TiO
2powder be placed in respectively 120 DEG C baking oven dry 3 hours, to remove surface moisture, for subsequent use.
Get the TiO that 10g is dried
2nucleus (particle diameter 1.2mm standard No. GB1706-2006) adds in bowling machine, in bowling machine, then add the TiO of oven dry with the constant speed of 62.5g/min simultaneously
2powder, adds pure water with the constant speed of 32.5g/min, adds starch adesive and add cerous nitrate saturated solution with the speed of change with the constant speed of 22.5g/min.Wherein, the speed that adds of cerous nitrate saturated solution meets increment type quadratic function v
cerium increases=-0.027+0.074t
2(v
cerium increasesspeed is added, g/min for cerous nitrate saturated solution), obtain through 20min the carrier predecessor that particle diameter is about 6mm.Adopt the mode of temperature programming to be warmed up to 70 DEG C with 55 DEG C/h the carrier predecessor of gained, and continue oven dry 6 hours at such a temperature.By the material roasting 3 hours at 800 DEG C after drying, after being cooled to room temperature, obtain carrier.
Getting 347g nickel nitrate is dissolved in 100g deionized water completely, then impregnated in the above-mentioned prepared carrier of 30g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 60 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 600 DEG C, obtains the catalyst prod of co-catalyst increment type distribution.After testing, in the catalyst prod of gained, the distribution of cerium meets functional equation: C
increase progressively=-0.121+0.336R
2; And the content of nickel element is 70wt%, the content of Ce elements is 3wt%.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, difference is:
Getting 421g nickel nitrate is dissolved in 120g deionized water completely, then impregnated in the carrier of 15g, makes in whole catalyst, and the content of carrier is 11wt%, and the content of major catalyst is 85wt%.
Obtain the catalyst prod that co-catalyst is increment type distribution along the radial direction of described catalyst granules.After testing, in the catalyst prod of gained, the distribution of samarium meets functional equation: C
samarium increases=-0.194+0.774R
2; And the content of nickel element is 85wt%, the content of samarium element is 4wt%.
Embodiment 5
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, difference is:
The mode of temperature programming is adopted to be warmed up to 80 DEG C with the speed of 60 DEG C/h the carrier predecessor of gained.
Obtain the catalyst prod that co-catalyst is increment type distribution along the radial direction of described catalyst granules.After testing, in the catalyst prod of gained, the distribution of samarium meets functional equation: C
samarium increases=-0.117+0.468R
2; And the content of nickel element is 35wt%, the content of samarium element is 4wt%.
Embodiment 6
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, difference is:
Material after drying is exposed in air, thermal decomposition 4 hours at 200 DEG C.
Obtain the catalyst prod that co-catalyst is increment type distribution along the radial direction of described catalyst granules.After testing, in the catalyst prod of gained, the distribution of samarium meets functional equation: C
samarium increases=-0.194+0.774R
2; And the content of nickel element is 35wt%, the content of samarium element is 4wt%.
Embodiment 7
By ZrO
2nucleus and powder be placed in the baking oven 3 hours of 120 DEG C, to remove surface moisture.Get 10gZrO
2nucleus (particle diameter 1.5mm standard No. HG/T2713-2004) adds in bowling machine, then in bowling machine, adds ZrO with the constant speed of 49.86g/min simultaneously
2powder, adds pure water with the constant speed of 25g/min, and add starch adesive with the constant speed of 24.17g/min and add manganese nitrate saturated solution with the speed of change, wherein, the speed that adds of manganese nitrate saturated solution meets increment type quadratic function v
manganese increases=-0.0002+0.0003t
2(v
manganese increasesspeed is added, g/min for manganese nitrate saturated solution), obtain through 60min the carrier predecessor that particle diameter is about 10mm.Adopt the mode of temperature programming to be warmed up to 60 DEG C with the speed of 30 DEG C/h the carrier predecessor of gained, and continue oven dry 6 hours at such a temperature.By the material roasting 4 hours at 600 DEG C after drying, obtain carrier.
Getting 100g nickel nitrate is dissolved in 68g deionized water completely, then impregnated in the above-mentioned prepared carrier of 80g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 500 DEG C, obtains the catalyst prod of co-catalyst increment type distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst manganese meets functional equation: C
manganese increases=-0.007+0.012R
2; And the content of nickel element is 20wt%, the content of manganese element is 0.5wt%.
Embodiment 8
The nucleus of MgO and powder are placed in the baking oven 3 hours of 120 DEG C, to remove surface moisture.Getting 10gMgO nucleus (particle diameter 1mm standard No. HG/T3928-2012) adds in bowling machine, then in bowling machine, add MgO powder with the constant speed of 41.7g/min simultaneously, pure water is added with the constant speed of 12.5g/min, add starch adesive with the constant speed of 25.83g/min and add cerous nitrate saturated solution with the speed of change, wherein, the speed that adds of cerous nitrate saturated solution meets decrescendo quadratic function v
cerium subtracts=0.108-0.017t
2(v
cerium subtractsspeed is added, g/min for cerous nitrate saturated solution), obtain through 30min the carrier predecessor that particle diameter is about 5mm.Adopt the mode of temperature programming to be warmed up to 160 DEG C with the speed of 80 DEG C/h the carrier predecessor of gained, and continue oven dry 4 hours at such a temperature.By the material roasting 5 hours at 500 DEG C after drying, obtain carrier.
Getting 157g nickelous sulfate is dissolved in 392g deionized water completely, then impregnated in the above-mentioned prepared carrier of 65g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 500 DEG C, obtains the catalyst prod of co-catalyst decrescendo distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst cerium meets functional equation: C
cerium subtracts=4.839-0.774R
2; And the content of nickel element is 35wt%, the content of Ce elements is 4wt%.
Embodiment 9
By Al
2o
3nucleus and powder be placed in the baking oven 3 hours of 120 DEG C, to remove surface moisture.Get 10gAl
2o
3nucleus (particle diameter 0.8mm standard No. HG/T3927-2007) adds in bowling machine, then in bowling machine, adds Al with the constant speed of 31.25g/min simultaneously
2o
3powder, adds pure water with the constant speed of 12.5g/min, and add starch adesive with the constant speed of 6.25g/min and add samaric nitrate saturated solution with the speed of change, wherein, the speed that adds of samaric nitrate saturated solution meets decrescendo quadratic function v
samarium subtracts=0.084-0.021t
2(v
samarium subtractsspeed is added, g/min for samaric nitrate saturated solution), obtain through 40min the carrier predecessor that particle diameter is about 4mm.Adopt the mode of temperature programming to be warmed up to 150 DEG C with the speed of 90 DEG C/h the carrier predecessor of gained, and continue oven dry 5 hours at such a temperature.By the material roasting 6 hours at 600 DEG C after drying, obtain carrier.
Getting 112g nickelous sulfate is dissolved in 280g deionized water completely, then impregnated in the above-mentioned prepared carrier of 75g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 500 DEG C, obtains the catalyst prod of co-catalyst decrescendo distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst samarium meets functional equation: C
samarium subtracts=15.121-3.78R
2; And the content of nickel element is 25wt%, the content of samarium element is 10wt%.
Embodiment 10
By TiO
2nucleus and powder be placed in the baking oven 3 hours of 120 DEG C, to remove surface moisture.Get 10gTiO
2nucleus (particle diameter 1.2mm, standard No. GB1706-2006) adds in bowling machine, then in bowling machine, adds TiO with the constant speed of 31.25g/min simultaneously
2powder, adds pure water with the constant speed of 11.25g/min, and add starch adesive with the constant speed of 17.5g/min and add lanthanum nitrate saturated solution with the speed of change, wherein, the speed that adds of lanthanum nitrate saturated solution meets decrescendo quadratic function v
lanthanum subtracts=0.102-0.011t
2(v
lanthanum subtractsspeed is added, g/min for lanthanum nitrate saturated solution), obtain through 40min the carrier predecessor that particle diameter is about 6mm.Adopt the mode of temperature programming to be warmed up to 150 DEG C with 100 DEG C/h the carrier predecessor of gained, and continue oven dry 4 hours at such a temperature.By the material roasting 3 hours at 500 DEG C after drying, obtain carrier.
Getting 313g nickelous sulfate is dissolved in 783g deionized water completely, then impregnated in the above-mentioned prepared carrier of 30g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 500 DEG C, obtains the catalyst prod of co-catalyst decrescendo distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst lanthanum meets functional equation: C
lanthanum subtracts=3.024-0.336R
2; And the content of nickel element is 70wt%, the content of lanthanum element is 3wt%.
Embodiment 11
By SiO
2nucleus and powder be placed in the baking oven 3 hours of 120 DEG C, to remove surface moisture.Get 10gSiO
2nucleus (particle diameter 1.5mm standard No. HG/T2765.3-2005) adds in bowling machine, then in bowling machine, adds SiO with the constant speed of 36g/min simultaneously
2powder, adds pure water with the constant speed of 18g/min, and add starch adesive with the constant speed of 17.7g/min and add manganese nitrate saturated solution with the speed of change, wherein, the speed that adds of manganese nitrate saturated solution meets decrescendo quadratic function v
manganese subtracts=0.006-0.0003t
2(v
manganese subtractsspeed is added, g/min for manganese nitrate saturated solution), the carrier predecessor that particle diameter is about 9mm was obtained through 60 minutes.Adopt the mode of temperature programming to be warmed up to 140 DEG C with 90 DEG C/h the carrier predecessor of gained, and continue oven dry 4 hours at such a temperature.By the material roasting 4 hours at 600 DEG C after drying, obtain carrier.
Getting 50g nickel nitrate is dissolved in 14g deionized water completely, then impregnated in the above-mentioned prepared carrier of 90g.Then the material after dipping is placed in the baking oven of 100 DEG C, adopt the mode of programmed cooling to cool to equilibrium temperature 40 DEG C with the speed of 30 DEG C/h from 100 DEG C, total drying time is 5 hours.Material after drying is exposed in air, thermal decomposition 2 hours at 500 DEG C, obtains the catalyst prod of co-catalyst decrescendo distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst manganese meets functional equation: C
manganese subtracts=0.335-0.017R
2; And the content of nickel element is 10wt%, the content of manganese element is 0.5wt%.
Embodiment 12
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, difference is:
Nucleus and carrier matrix material are TiO
2-Al
2o
3.
Obtain the catalyst prod that co-catalyst is increment type distribution along the radial direction of described catalyst granules.After testing, in the catalyst prod of gained, the distribution of samarium meets functional equation: C
samarium increases=-0.194+0.774R
2; And the content of nickel element is 35wt%, the content of samarium element is 4wt%.
Embodiment 13
Adopt the method Kaolinite Preparation of Catalyst similar to embodiment 10, difference is:
Nucleus and carrier matrix material are ZrO
2-Al
2o
3; Thermal decomposition 2 hours at 600 DEG C.
Obtain the catalyst prod of co-catalyst decrescendo distribution.After testing, in the catalyst prod of gained, the CONCENTRATION DISTRIBUTION of co-catalyst cerium meets functional equation: C
cerium subtracts=4.839-0.774R
2; And the content of nickel element is 35wt%, the content of Ce elements is 4wt%.
Comparative example 1
With reference to the method Kaolinite Preparation of Catalyst described in embodiment 1, with the method described in embodiment 1 unlike, in bowling machine, do not add samaric nitrate saturated solution, the content finally obtaining nickel element be 50.13wt% not containing the catalyst of co-catalyst.
Comparative example 2
With reference to the method Kaolinite Preparation of Catalyst described in embodiment 1, with the method described in embodiment 1 unlike, lanthanum nitrate saturated solution 30min is altogether added with constant speed 97.12g/min in bowling machine, the content finally obtaining nickel element is 30wt%, and the content of lanthanum element is the co-catalyst of 3wt% is equally distributed catalyst.
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 1 in patent application CN102513119A, the La of the NiO of consisting of of gained catalyst: 20wt%, 33wt%
2o
3, the graphite of 7wt% and the Al of 40wt%
2o
3.Wherein co-catalyst lanthanum is for being uniformly distributed.
Composition and the relevant parameter of catalyst prepared in above-described embodiment 1-13 and comparative example 1-3 are as shown in table 1.Catalyst prepared in embodiment 1-13 and comparative example 1-3 is applied to following pilot experiment 1 and pilot experiment 2 (experiment condition sees below) respectively, and the concentration (ppm) detecting the CO that pilot scale 1 exports and pilot scale 2 exports is as shown in table 1 below.
Table 1
Note: "+" represents the outer concentration of co-catalyst comparatively interior floor height, i.e. increment type; Comparatively internal layer is low for the outer concentration of "-" expression co-catalyst, i.e. decrescendo.
The experiment condition of pilot experiment 1 and embodiment are: loaded by above-mentioned catalyst 100ml in reactor, H at 500 DEG C
2after reduction, switch to the rich hydrogen raw material of the CO containing 2000ppm, at 250 DEG C, 2.8MPa (gauge pressure), gas space velocity 400h
-1reaction condition under, after the reactor of above-mentioned catalyst is housed, chromatogram detects the concentration of total oxycarbide CO in gas.
The experiment condition of pilot experiment 2 and embodiment are: loaded by above-mentioned catalyst 100ml in reactor, H at 500 DEG C
2after reduction, switch to the rich hydrogen raw material of the CO containing 2000ppm, at 250 DEG C, 2.8MPa (gauge pressure), gas space velocity 4000h
-1reaction condition under, after the reactor of above-mentioned catalyst is housed, chromatogram detects the concentration of total oxycarbide CO in gas.
Data from table 1 can be seen, during catalyst (embodiment 1-13) prepared by the present invention exports when removing the CO of trace in hydrogen, the content of CO is far smaller than catalyst (comparative example 1-3) prepared by additive method, can prove that the catalyst of co-catalyst non-uniform Distribution prepared by method of the present invention has good methanation reaction catalytic activity and the effect of purified hydrogen.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a catalyst for co-catalyst non-uniform Distribution, is characterized in that, described catalyst comprises carrier and load major catalyst on this carrier, and described carrier comprises nucleus, carrier matrix material and co-catalyst; The CONCENTRATION DISTRIBUTION of described co-catalyst is heterogeneous in the catalyst, outer surface along described nucleus points to the direction of the outer surface of described catalyst, described co-catalyst be distributed as increment type or decrescendo, with the total amount of described catalyst for benchmark, the content of described major catalyst is 10-90wt%, and the content of described carrier is 10-90wt%.
2. catalyst according to claim 1, wherein, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, in the skin of described catalyst co-catalyst concentration ratio described in catalyst internal layer in the concentration height 0.2-12wt% of co-catalyst;
When the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, in the skin of described catalyst co-catalyst concentration ratio described in catalyst internal layer in the low 0.2-12wt% of concentration of co-catalyst.
3. catalyst according to claim 2, wherein, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, the CONCENTRATION DISTRIBUTION of described co-catalyst meets with following formula 1:
C
help increasing=a × R
2+ b × R+c formula 1
Wherein, C
help increasingfor the concentration of co-catalyst, unit is wt%; The position of R corresponding to the concentration of corresponding co-catalyst is to the distance of nucleus outer surface, and unit is mm; A is zero or normal number, and b is constant, and c is zero or negative constant;
When the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, the CONCENTRATION DISTRIBUTION of described co-catalyst meets with following formula 2:
C
help and subtract=-d × R
2-e × R+f formula 2
Wherein, C
help and subtractfor the concentration of co-catalyst, unit is wt%; The position of R corresponding to the concentration of corresponding co-catalyst is to the distance of nucleus outer surface, and unit is mm; D is zero or normal number, and e is constant, and f is zero or negative constant.
4. catalyst according to claim 1, wherein, with the total amount of described catalyst for benchmark, the content of described major catalyst is 20-80wt%, and the content of described carrier is 20-80wt%.
5. according to the catalyst in claim 1-4 described in any one, wherein, described co-catalyst is at least one in alkali metal, alkaline-earth metal, transition metal and rare earth metal;
Preferably, described co-catalyst is at least one in following metal: sodium, magnesium, barium, manganese, lanthanum, cerium, samarium, europium, gadolinium, erbium, thulium, molybdenum and yttrium;
More preferably, in the catalyst, the content of described co-catalyst is 0.1-20wt%, is more preferably 0.5-15wt%.
6. according to the catalyst in claim 1-4 described in any one, wherein, described major catalyst is nickel.
7. the preparation method of the catalyst of the co-catalyst non-uniform Distribution in claim 1-6 described in any one, it is characterized in that, the method comprises the following steps: under the existence of nucleus, with rolling ball method, water, carrier matrix material, binding agent and the saturated solution containing cocatalyst are mixed continuously, what control the saturated solution containing cocatalyst adds speed, and the CONCENTRATION DISTRIBUTION obtaining wherein co-catalyst is the carrier predecessor of increment type and/or decrescendo; Described carrier predecessor is carried out the first oven dry successively and roasting obtains carrier; The carrier obtained is contacted with the solution containing major catalyst, then carries out the second oven dry and thermal decomposition.
8. method according to claim 7, wherein, the particle diameter of described nucleus is 0.5-1.5mm;
Preferably, be 100 parts by weight with total consumption of described nucleus and described carrier matrix material, the consumption of described water is 10-60 weight portion, the consumption of described binding agent is 20-50 weight portion and the described consumption containing the saturated solution of cocatalyst is 1-40 weight portion, and the weight ratio of the consumption of described nucleus and described carrier matrix material is 1:50-300.
9. the method according to claim 7 or 8, wherein, when the CONCENTRATION DISTRIBUTION of described co-catalyst is increment type, the adding speed and can meet with following formula 3 of the described saturated solution containing cocatalyst,
V
help increasing=g × t
2+ h × t+i formula 3
Wherein, v
help increasingadd speed for the described saturated solution containing cocatalyst, unit is g/min; T is the interpolation time of the saturated solution containing cocatalyst, and unit is min; G is zero or normal number, and h is constant, and i is zero or negative constant;
When the CONCENTRATION DISTRIBUTION of described co-catalyst is decrescendo, the adding speed and can meet with following formula 4 of the described saturated solution containing cocatalyst,
V
help and subtract=-j × t
2-k × t+l formula 4
Wherein, v
help and subtractadd speed for the described saturated solution containing cocatalyst, unit is g/min; T is the interpolation time of the saturated solution containing cocatalyst, and unit is min; J is zero or normal number, and k is constant, and l is zero or negative constant.
10. the method according to claim 7 or 8, wherein, when in described carrier predecessor, the CONCENTRATION DISTRIBUTION of co-catalyst is increment type, the described first condition of drying comprises: drying and warning speed is 30-60 DEG C/h, oven dry equilibrium temperature is 60-100 DEG C, and the time is 4-6h;
When in described carrier predecessor, the CONCENTRATION DISTRIBUTION of co-catalyst is decrescendo, the described first condition of drying comprises: drying and warning speed is 70-100 DEG C/h, and oven dry equilibrium temperature is 100-160 DEG C, and the time is 1-3h.
11. methods according to claim 7 or 8, wherein, the condition of described roasting comprises: temperature is 200-1000 DEG C, and the time is 2-8h;
Described second condition of drying comprises: drying rate of temperature fall is 30-80 DEG C/h, and oven dry equilibrium temperature is 40-160 DEG C, and the time is 1-6h;
Preferably, the condition of described thermal decomposition comprises: temperature is 200-600 DEG C, and the time is 2-8h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041968A (en) * | 1988-10-19 | 1990-05-09 | 中国科学院大连化学物理研究所 | Water at atmospheric pressure gas methanation active non-uniform type catalyzer and manufacture method thereof |
| US20030086866A1 (en) * | 2001-10-26 | 2003-05-08 | Wangerow James R. | Compact combined shift and selective methanation reactor for co control |
| CN102015069A (en) * | 2008-04-23 | 2011-04-13 | 罗地亚管理公司 | Composition containing zirconium, cerium and yttrium oxides having a high reducibility, method for preparing same and use thereof in catalysis |
-
2014
- 2014-08-13 CN CN201410397850.XA patent/CN105435860A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041968A (en) * | 1988-10-19 | 1990-05-09 | 中国科学院大连化学物理研究所 | Water at atmospheric pressure gas methanation active non-uniform type catalyzer and manufacture method thereof |
| US20030086866A1 (en) * | 2001-10-26 | 2003-05-08 | Wangerow James R. | Compact combined shift and selective methanation reactor for co control |
| CN102015069A (en) * | 2008-04-23 | 2011-04-13 | 罗地亚管理公司 | Composition containing zirconium, cerium and yttrium oxides having a high reducibility, method for preparing same and use thereof in catalysis |
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