CN104841448B - Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor - Google Patents
Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor Download PDFInfo
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Abstract
The invention belongs to the field of methanation catalysis, and relates to an organic silicon waste contact body borne nickel-based methanation catalyst and a preparation method therefor. The catalyst comprises a carrier, an active component, a modifier and an auxiliary agent, wherein the carrier is an organic silicon waste contact body, the modifier is a porous inorganic oxide, the active component is Ni, and the auxiliary agent is a transition metal oxide. By using the porous inorganic oxide modifier in the invention, on one hand, the interacting force between the active component and the carrier is enhanced, and the dispersibility of the active component is improved; on the other hand, the inorganic oxide dispersed in the active component further serves as a physical barrier, and suppresses agglomeration and sintering of Ni particles. The catalyst obtained in the invention is high in catalytic activity, high in anti-carbon deposition and anti-sintering performance and low in cost, and particularly suitable for methanation reaction systems of high-concentration CO.
Description
Technical field
The invention belongs to methanation catalyst field, in particular it relates to a kind of load of abandoned catalyst in direct synthesis methylchlorosilane is Ni-based
Methanation catalyst and preparation method thereof.
Background technology
China is the country of " rich coal, oil-poor, few gas ".Coal in the primary energy consumption structure of China in occupation of
Main status.But, consume coal 80% or so is directly converted by burning, and heat utilization rate is low, while discharging a large amount of pollutant.
Therefore, develop efficient, low-carbon (LC), clean coal resources to be of great significance using technology tool.
The gas that coal or biomass pyrolytic, gasification are obtained is mainly contained into H2And CO, coking industry coke-stove gas it is main
It is also H that composition is2And CO, these mixed gas containing CO be able to can give birth to after technique through converting and purifying etc. by methanation reaction
Into CH4.This can not only promote the high effect cleaning of coal to comprehensively utilize and improve fuel gas calorie density, while to fill up me
State's Natural Gas Demand breach provides a practicable approach.Methanation relates generally to following reaction：
CO+3H2→CH4+H2O ΔrHm=-206kJ/mol
The reaction is strong exothermal reaction, and the instantaneous temperature runaway in beds can make methanation catalyst sinter and lose work
Property.Further, since methanation reaction is easy to make in itself catalyst because of carbon distribution inactivation, the anti-carbon performance of catalyst and high temperature resistant
Performance will directly affect the life-span of catalyst.Therefore, a kind of catalysis activity is developed high, and being capable of long-time stable at high temperature
The methanation catalyst of work is one of key factor of synthesis gas methanation process.
Although quite a lot of with regard to the research of methanation catalyst both at home and abroad, there is partial catalyst to have on a large scale
The use experience of industrial project or demonstrative project, but not all methanation catalyst is suitable for natural gas from coal item
Mesh.The CO hydrogenation methanation catalysts of reporting are mostly for removing rich H2A small amount of CO impurity in system, conventional catalysis
Agent is Ni the and Ru transition metal being carried on oxide, and the oxide carrier of employing has Al2O3、SiO2、TiO2、ZrO2、MgO
Deng.These catalyst are in synthesis NH3And can reach substantially in the methanation reaction application of fuel cell industries removing low concentration CO
To ideal effect, but CO concentration is higher in the synthesis gas methanation reaction that obtains of coal or gasification of biomass, methanation
Exothermic heat of reaction is strong, and carbon distribution and sintering phenomenon can be made serious.Therefore, new, urging suitable for high concentration CO methanation is developed
Agent has great importance.
At present, the minority offshore company such as rope company of Top of Denmark, British Gas company, German LURGI has had phase
To ripe High Temperature High Pressure synthesis gas methanation catalyst (such as CRG, MCR).China is catalyzed with regard to synthesis gas methanation reaction
Agent is the nickel of different content, molybdenum isoreactivity component in load with porous oxides such as aluminium oxide, silicon oxides as carrier mostly, and auxiliary
With some auxiliary agents such as transition metal, alkali metal, alkaline-earth metal and rare-earth oxide etc..As patent CN101380581A,
CN1041968A, CN101745401A and CN110132A etc..The methanation catalyst of existing patent introduction is mostly to adopt porous
Oxide is carrier, and material thermal conductivity is poor, and easily local temperature is too high in formation beds, causes sintering of catalyst, urges
Change efficiency and decline even inactivation.Therefore, the good methanation catalyst material of heat conductivility is developed, contributes to extending the longevity of catalyst
Life.
Organosilicon industry is prepared and can produce in methylchlorosilane technique substantial amounts of waste catalyst.These waste catalysts are by porous
Silicon, copper, carbon and micro zinc composition, mean diameter is thinner, and exposure easily causes in atmosphere oxidation even to burn, environmental pollution
Seriously, while being also the hidden danger in safety in production.With the production-scale continuous expansion of China's organic silicon monomer, the amount of waste catalyst
It is continuously increased, the process and utilization always China's silicone industry sustainable development problem demanding prompt solution to waste catalyst.At present,
Process to waste catalyst both at home and abroad has carried out substantial amounts of research.Patent US4758352 is carried out to reclaiming silicon, copper from waste catalyst
Research, deep conversion is carried out for white carbon, SiCl by waste catalyst4、HSiCl3, the product such as phenyl chlorosilane.For the ease of transport and
Process, by the process of waste catalyst deactivation, such as patent US4892694 is processed into stable granule or bead.Although to useless
The process of contact has carried out substantial amounts of research, but it is serious and product attached to yet suffer from complex disposal process, secondary pollution
Value added relatively low the problems such as.Therefore, in the urgent need to finding a kind of simple, cleaning, while can be in the method for higher value application waste catalyst.
The content of the invention
For the deficiency that above-mentioned technology is present, the present invention using heat stability is good, pyroconductivity is high, it is cheap and easy to get organic
Silicon waste catalyst is carrier, with reference to the surface modification technology of porous inorganic oxide, has obtained a kind of abandoned catalyst in direct synthesis methylchlorosilane load
Ni-based methanation catalyst, not only increases the anti-sintering and anti-carbon performance of catalyst, and realizes the high level of waste catalyst
Change and utilize.
Based on this, an object of the present invention is to provide a kind of Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load
Agent.
To achieve these goals, present invention employs following technical scheme：
A kind of Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load, the catalyst includes active component, carrier, changes
Property agent and auxiliary agent, wherein, the active component is nickel；Carrier is abandoned catalyst in direct synthesis methylchlorosilane；Modifying agent is porous inorganic oxide,
Auxiliary agent is transition metal oxide.
Preferably, with the content meter of oxide, the gross mass of catalyst is 100%, and each component accounts for catalyst gross mass
Mass percent is respectively：
Active component 10～70%
Auxiliary agent 0.5～15%
Carrier and modifying agent surplus, modifying agent is 0.05～2 with the mass ratio of carrier.
The active component nickel in terms of oxide, the content of active component is, for example, 15%, 20%, 25%, 30%,
35%th, 40%, 45%, 50%, 55%, 60% or 65%.For low temperature methanation catalyst process, the present invention preferably active component
Mass percent be 10～25%；For high-temperature methanation process, the mass percent of the present invention preferably active component is 25
～60%, and for 30～50% economical rationality the most.
The content of the auxiliary agent is, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%,
12%th, 13% or 14%.
The mass ratio of the modifying agent and carrier is, for example, 0.08,0.1,0.3,0.5,0.7,0.9,1.1,1.3,1.5,
1.7 or 1.9.For low temperature methanation catalyst process, the present invention preferably modifying agent and the mass ratio of carrier are 0.05～0.3；It is right
In high-temperature methanation process, the present invention preferably modifying agent and the mass ratio of carrier are 0.25～2.
The Ni-based methanation catalyst of the abandoned catalyst in direct synthesis methylchlorosilane load of the present invention, using with excellent heat stability and heat
The abandoned catalyst in direct synthesis methylchlorosilane of conductivity be carrier, it is possible to increase the heat conductivility of catalyst, so as to improve catalyst anti-sintering and
Carbon accumulation resisting ability.On the one hand porous inorganic oxide modifying agent can strengthen the interaction force between active component and carrier,
The dispersion of active component Ni granule is improved, another aspect porous inorganic oxide is interspersed among between active component Ni granule or covered
It is placed on Ni granules, moreover it is possible to play a part of physical barrier, suppresses reunion and the sintering of Ni granules.Auxiliary agent transition metal for
Methanation catalyst with nickel as active component has the effect of electronic auxiliary and structural promoter concurrently, and on the one hand providing electronics contributes to
In the dissociation of catalyst surface, plus the carrying out of fast response, in addition, interacting with NiO, prevent growing up for Ni crystal grain to CO.At this
In the catalyst of invention, need to control the ratio between active component and auxiliary agent, auxiliary agent content is too low, and catalyst activity is improved not
Substantially；Conversely, excessive auxiliary agent is then easily caused part Ni active sites being capped, reduce catalyst catalytic performance.
Preferably, the modifying agent is Al2O3、TiO2、ZrO2, MgO or SiO2Any one in or at least two
Mixture.
Preferably, the auxiliary agent is V2O5、Cr2O3、CeO2、La2O3Or MnO2Any one in or at least two
Mixture.
In the present invention, the abandoned catalyst in direct synthesis methylchlorosilane is to urge for raw material, copper or its compound using silicon for silicone industry
The solid residue produced during agent production organosilicon methyl chlorosilane monomer, mainly contain one kind in Si, Cu and C etc. or
One or more in the components such as several and micro Zn, Fe, Al and Sn.Wherein Si contents are 50～95% (weight ratios),
Cu contents are in 1～20% (weight ratio), C content 1～20% (weight ratio).
Preferably, the abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
Preferably, the pretreatment is comprised the following steps：
A () is by abandoned catalyst in direct synthesis methylchlorosilane at 300～700 DEG C (such as 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C
Or 650 DEG C) 0.5～5h of calcining (such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h), then crush and screen out grain
Footpath is 0.5～100 μm of abandoned catalyst in direct synthesis methylchlorosilane；
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filter, be dried, ball milling, and Ball-milling Time is
12～24h (such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h).
Preferably, the acid is H2SO4、HCl、H3PO4、HNO3Or in acetic acid any one or at least two mixing
Thing.
Preferably, the concentration of the acid is 0.1～4.0mol/L.
Preferably, acid amount needed for institute's containing metal oxide is completely dissolved during the usage amount of the acid is to make abandoned catalyst in direct synthesis methylchlorosilane
1～3 times.
Preferably, the number of times of the pickling is at least one times.
Preferably, the pickling time is 2～12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h.
Preferably, the baking temperature be 100～200 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C or 190 DEG C, the time be 5～24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h.
The second object of the present invention is to provide a kind of Ni-based methanation of abandoned catalyst in direct synthesis methylchlorosilane load as above to urge
The preparation method of agent, the method comprising the steps of：
By the raw material needed for synthesizing activity component, auxiliary agent and modifier components, according to the composition of catalyst, cocurrent is added to be had
In the dispersion liquid of machine silicon waste catalyst, (i.e. above-mentioned four kinds of raw materials add the dispersion of abandoned catalyst in direct synthesis methylchlorosilane simultaneously while Deca precipitant
In liquid), and control system pH be 7.5～11 (such as 7.8,8.2,8.5,8.8,9.2,9.5,9.8,10,10.3,10.6 or
10.9), make precipitation by metallic ion completely, obtain Catalyst precursor solutions, then filter, wash, be dried, calcine and reduce,
Obtain the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
In the present invention, the abandoned catalyst in direct synthesis methylchlorosilane is to urge for raw material, copper or its compound using silicon for silicone industry
The solid residue produced during agent production organosilicon methyl chlorosilane monomer, mainly contain one kind in Si, Cu and C etc. or
One or more in the components such as several and micro Zn, Fe, Al and Sn.Wherein Si contents are 50～95% (weight ratios),
Cu contents are in 1～20% (weight ratio), C content 1～20% (weight ratio).
Preferably, the abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
Preferably, the pretreatment is comprised the following steps：
A () is by abandoned catalyst in direct synthesis methylchlorosilane at 300～700 DEG C (such as 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C
Or 650 DEG C) 0.5～5h of calcining (such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h), then crush and screen out grain
Footpath is 0.5～100 μm of abandoned catalyst in direct synthesis methylchlorosilane；
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filter, be dried, ball milling, and Ball-milling Time is
12～24h (such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h).
Preferably, the acid is H2SO4、HCl、H3PO4、HNO3Or in acetic acid any one or at least two mixing
Thing.
Preferably, the concentration of the acid is 0.1～4.0mol/L.
Preferably, acid amount needed for institute's containing metal oxide is completely dissolved during the usage amount of the acid is to make abandoned catalyst in direct synthesis methylchlorosilane
1～3 times.
Preferably, the number of times of the pickling is at least one times.
Preferably, the pickling time is 2～12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h.
Preferably, the baking temperature be 100～200 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C or 190 DEG C, the time be 5～24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h.
Preferably, the preparation method of the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid is：
Abandoned catalyst in direct synthesis methylchlorosilane is dispersed in water, be heated to 40～90 DEG C (such as 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C,
70 DEG C, 75 DEG C, 80 DEG C or 85 DEG C), then adopt the pH value of precipitant regulation system for 7.5～11 (such as 7.8,8.2,8.5,
8.8th, 9.2,9.5,9.8,10,10.3,10.6 or 10.9), obtain the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, the precipitant is NaOH, KOH, Na2CO3、K2CO3, ammonium carbonate and ammonia aqueous solution in it is any
It is a kind of or at least two combination, its concentration be 0.2～2.0mol/L.
Preferably, as a solution cocurrent is added the raw material needed for synthesizing activity component, auxiliary agent and modifier components
In the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, the raw material needed for synthesis modification agent selected from the nitrate of aluminum, magnesium, zirconium, titanium or silicon, carbonate, chloride,
Silicate or ester.
Preferably, the raw material needed for synthesizing activity component is any one in nickel nitrate, nickel sulfate, Nickel dichloride. or nickel acetate
Kind or at least two combination.
Preferably, the raw material needed for additive synthesis is selected from the nitrate or carbonate of chromium, manganese, cerium or lanthanum, or acetylacetone,2,4-pentanedione
Vanadyl.
Preferably, nitric acid dissolving is added when the carbonate of the carbonate and chromium of aluminum, magnesium, zirconium or titanium, manganese, cerium or lanthanum is used
Form solution.
Preferably, it is dissolved in when the chloride of titanium, ester or vanadyl acetylacetonate are used in ethanol and forms solution.
Preferably, the Deca raw material under conditions of stirring, mixing time be 3～10h, such as 4h, 5h, 6h, 7h, 8h or
9h。
Preferably, the calcining heat is 400～700 DEG C, and such as 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 650 DEG C are forged
The burning time is 2～6h, such as 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h.Control during calcining temperature for 400-～700 DEG C,
Calcining heat is too low, and carrier will be made to weaken with the interphase interaction of active component, and active component is easy to run off, and temperature is too high, activity
Component is substantially reunited, it is difficult to reduced, and makes catalyst activity reduction.
Preferably, the reduction temperature be 400～800 DEG C, such as 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700
DEG C or 750 DEG C, the recovery time be 1～3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8h.
The preparation method of the Ni-based methanation catalyst of exemplary abandoned catalyst in direct synthesis methylchlorosilane load is comprised the following steps：
1) pretreatment of abandoned catalyst in direct synthesis methylchlorosilane carrier：
1-1) by abandoned catalyst in direct synthesis methylchlorosilane at 300-700 DEG C, calcine 0.5～5h, then crush and screen out particle diameter for 0.5～
100 μm of abandoned catalyst in direct synthesis methylchlorosilane；
1-2) abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out into pickling, then filter, be dried and ball milling, Ball-milling Time
For 12～24h；
2) preparation of catalyst：
2-1) by step 1) in the pretreated abandoned catalyst in direct synthesis methylchlorosilane that obtains be dispersed in water, be heated to 40～90 DEG C,
Adopt the pH value of precipitant regulation system for 7.5～11, obtain the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane；
2-2) by the raw material needed for synthesizing activity component, auxiliary agent and modifying agent, according to the composition of catalyst, it is respectively configured to
Solution, cocurrent is added to 2-1) in the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid that obtains, while Deca precipitant, and control system pH value is
7.5-11,3～10h is stirred, obtain catalyst precursor mixed liquor；
2-3) catalyst precursor is filtered, washed and dried, products therefrom calcines 2～6h at 400～700 DEG C, it
At 400～800 DEG C, 1～3h is reduced, form the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
Compared with the prior art, the present invention has the advantages that：
1st, the present invention is used as methanation catalyst carrier using cheap abandoned catalyst in direct synthesis methylchlorosilane, and the catalyst prepared is urged
Change activity height, good stability, anti-sintering and anti-carbon performance are strong, be particularly suited for the methanation catalyst reaction of high concentration CO, table
Reveal good activity and stability.
2nd, methanation catalyst prepared by the present invention, low raw-material cost, reduce the cost of catalyst, operational approach letter
It is single, it is easy to large-scale production.
3rd, by the CO methanations of the catalyst application high concentration, not only light-off temperature is low, at low temperature with high activity, and
And the activity of catalyst remains to keep stable under high temperature.
Description of the drawings
Fig. 1 is the XRD spectra of the abandoned catalyst in direct synthesis methylchlorosilane after the process that embodiment 1 is obtained and pure silicon；
Fig. 2 is the TEM figures that the catalyst amplification of the abandoned catalyst in direct synthesis methylchlorosilane load that comparative example 1 is obtained is 100000；
Fig. 3 is the TEM figures that the catalyst amplification of the abandoned catalyst in direct synthesis methylchlorosilane load that embodiment 2 is obtained is 100000；
Fig. 4 is embodiment 6 and 8 and certain commercial catalysts CH in methanation reaction life test4Yield with the time
Change.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：
1) the useless body of organosilicon is touched and is placed in Muffle furnace, 5h is calcined at 300 DEG C, then crushed, screen out particle diameter and be
0.5-100 μm of sample is standby；
2) abandoned catalyst in direct synthesis methylchlorosilane after the above-mentioned screenings of 10g is positioned in beaker, adds the nitric acid of 30mL 2mol/L, put
To on magnetic stirring apparatuss, 12h is stirred at 20 DEG C, the supernatant is poured in waste liquid bottle, is cleaned repeatedly with water afterwards, until cleaning mixture
For neutrality, then filter, by gained sample in 100 DEG C of oven drying 24h；Dried sample is placed in ball milling 12h on ball mill,
Gained silicon waste catalyst is named as WCM, and storage is good standby.
The preparation of catalyst：3.20g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-baths are quickly stirred
0.5h, by 3.10g Ni (NO3)2·6H2O, 0.21g La (NO3)3·6H2O is dissolved separately in 50mL water, by 0.95g
TiCl4It is dissolved in 50mL dehydrated alcohol, and configures the sal volatile of 0.5mol/L, is then added drop-wise to above-mentioned 4 kinds of solution cocurrents
In round-bottomed flask, pH value is detected with pH meter during Deca, its pH is controlled 8 or so, after 60 DEG C of stirring in water bath 8h, sucking filtration is washed
It is 7 or so to wash to pH, and the sample for obtaining is dried into 12h in 100 DEG C.Gained sample calcines 6h in air atmosphere at 400 DEG C, heats up
2 DEG C/min of speed, then in H2600 DEG C of reductase 12 h in atmosphere, the catalyst for obtaining is labeled as CAT-1.
X ' the Pert that the abandoned catalyst in direct synthesis methylchlorosilane carrier of above-mentioned process is produced in Dutch Panalytical companies (PANalytical)
XRD tests are carried out on PRO MPD type Multi-functional X ray diffractometers.
Fig. 1 gives the XRD spectra of the abandoned catalyst in direct synthesis methylchlorosilane carrier handled by embodiment 1 and pure silicon.Silicon after process
Waste catalyst carrier and pure silicon show identical characteristic diffraction peak, and the abandoned catalyst in direct synthesis methylchlorosilane purity after explanation is processed is very high.
Comparative example 1
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：
1) the useless body of organosilicon is touched and is placed in Muffle furnace, 5h is calcined at 300 DEG C, then crushed, screen out particle diameter for 0.5
～100 μm of sample is standby；
2) abandoned catalyst in direct synthesis methylchlorosilane after the above-mentioned screenings of 10g is positioned in beaker, adds the nitric acid of 30mL 2mol/L, put
To on magnetic stirring apparatuss, 12h is stirred at 20 DEG C, the supernatant is poured in waste liquid bottle, is cleaned repeatedly with water afterwards, until cleaning mixture
For neutrality, then filter, by gained sample in 100 DEG C of oven drying 24h；Dried sample is placed in ball milling 12h on ball mill,
Gained silicon waste catalyst is named as WCM, and storage is good standby.
The preparation of catalyst：3.20g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-baths are quickly stirred
0.5h, by 3.10g Ni (NO3)2·6H2O, in being dissolved in 50mL water, and configures the sal volatile of 0.5mol/L, then will be upper
State 4 kinds of solution cocurrents to be added drop-wise in round-bottomed flask, pH value is detected with pH meter during Deca, its pH is controlled 8 or so, 60 DEG C
After stirring in water bath 8h, filtering and washing to pH is 7 or so, and the sample for obtaining is dried into 12h in 100 DEG C.Gained sample is in air atmosphere
In calcine 6h, 2 DEG C/min of heating rate, then in H at 400 DEG C2600 DEG C of reductase 12 h in atmosphere, the catalyst for obtaining is labeled as
CAT-0。
Above-mentioned CAT-0 catalyst is observed into Ni in the JEM-2010F models transmission electron microscope that NEC company produces is having
Distribution situation on machine silicon waste catalyst, as a result illustrates that Ni crystallite dimensions prepared by this method are little and uniform.
Embodiment 2
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by the roasting of pretreatment silicon waste catalyst
Temperature is changed to 400 DEG C, and acid used replaces with HCl.
The preparation of catalyst：2.72g WCM are placed in the round-bottomed flask of 50mL deionized waters, 40 DEG C of water-baths are quickly stirred
0.5h, by 3.10g Ni (NO3)2·6H2O, 2.94g Al (NO3)3·9H2O, 0.33g 50wt%Mn (NO3)2It is dissolved separately in
In 50g water, and the NaOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, Deca mistake
PH value is detected with pH meter in journey, its pH is controlled 9 or so, after 40 DEG C of stirring in water bath 8h, filtering and washing to pH is 7 or so, will
The sample for obtaining is dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate in air atmosphere at 500 DEG C, then
In H2600 DEG C of reductase 12 h in atmosphere, the catalyst for obtaining is labeled as CAT-2.
Above-mentioned CAT-2 catalyst is observed into Ni in silicon in the JEM-2010F models transmission electron microscope that NEC company produces
Dispersion on waste catalyst and distribution, and aluminium oxide modifier distribution situation in the catalyst.As a result illustrate that Ni is brilliant in CAT-2
Particle size is little and is evenly distributed, and a modifier aluminium oxide part is evenly distributed on silicon waste catalyst, and a part intersperses among activity
Between component Ni granule or it is covered on Ni granules, therefore physical barrier can be played a part of, suppresses the reunion of Ni granules, burns
Knot.
Embodiment 3
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 700 DEG C, and acid used replaces with sulphuric acid.
The preparation of catalyst：2.72g WCM are placed in the round-bottomed flask of 50mL deionized waters, 90 DEG C of water-baths are quickly stirred
0.5h, by 3.10g Ni (NO3)2·6H2O, 2.55g Mg (NO3)2·6H2O, 0.2gCe (NO3)3·6H2O is dissolved separately in 50g
In water, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, are used during Deca
PH meter detects pH value, and its pH is controlled 8 or so, and after 8 hours, filtering and washing to pH is 7 or so to 90 DEG C of stirring in water bath, will be obtained
Sample in 100 DEG C of dryings 12 hours.Gained sample is calcined 2 hours in air atmosphere at 700 DEG C, 2 DEG C/min of heating rate, so
After H2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-3.
Embodiment 4
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with phosphoric acid.
The preparation of catalyst：2.72g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-baths are quickly stirred
0.5h, by 3.10g Ni (NO3)2·6H2O, 1.40g Zr (NO3)4·5H2O, 0.35g vanadyl acetylacetonate is dissolved separately in 50g
In water, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, are used during Deca
PH meter detects pH value, and its pH is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, will
To sample be dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate, Ran Houyu in air atmosphere at 400 DEG C
H2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-4.
Embodiment 5
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with acetic acid.
The preparation of catalyst：2.40g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-baths are quickly stirred
0.5h, by 1.56g Ni (NO3)2·6H2O, 5.88g Al (NO3)3·9H2O, 0.53gLa (NO3)3·6H2O is dissolved separately in
In 50g water, and the ammonia of 2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, and pH is used during Deca
Meter detection pH value, is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, by what is obtained
Sample is dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate, then in H in air atmosphere at 400 DEG C2Atmosphere
In 600 DEG C of reductase 12 h, the catalyst of preparation is labeled as CAT-5.
Embodiment 6
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with HCl.
The preparation of catalyst：2.60g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-bath uniform stirrings
0.5h, by 6.24g Ni (NO3)2·6H2O, 2.80g Zr (NO3)4·5H2O, 0.5g vanadyl acetylacetonate is dissolved separately in 50g
In water, and configure the K of 1mol/L2CO3 solution, then above-mentioned 4 kinds of solution cocurrents be added drop-wise in round-bottomed flask, use during Deca
PH meter detects pH value, is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, will be obtained
Sample be dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate, then in H in air atmosphere at 400 DEG C2
600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-6.
Embodiment 7
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with HCl.
The preparation of catalyst：2.20g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-bath uniform stirrings
0.5h, by 6.10g Ni (NO3)2·6H2O, 5.09g Mg (NO3)2·6H2O, 0.82g 50wt%Mn (NO3)2It is dissolved separately in
In 50g water, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, Deca process
Middle pH meter detects pH value, and its pH is controlled 10 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so,
The sample for obtaining is dried into 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate in air atmosphere at 400 DEG C；So
After H2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-7.
Embodiment 8
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with HCl.
The preparation of catalyst：2.08g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-bath uniform stirrings
0.5h, by 5.40g Ni (NO3)2·6H2O, 5.88g Al (NO3)3·9H2O, 0.8gCe (NO3)3·6H2O is dissolved separately in 50g
In water, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, are used during Deca
PH meter detects pH value, and its pH is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, will
To sample be dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate, Ran Houyu in air atmosphere at 400 DEG C
H2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-8.
Embodiment 9
The preparation of catalyst carrier (process of silicon waste catalyst)：It is the same with the process step of embodiment 1, simply will process organic
Organic solvent and acid used by silicon waste catalyst replaces with toluene and HCl.
The preparation of catalyst：2.08g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-bath uniform stirrings
0.5h, by 2.15g NiCl2·6H2O, 2.80g Zr (NO3)4·5H2O, 0.84gLa (NO3)3·6H2O is dissolved separately in 50g water
In, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, and pH is used during Deca
Meter detection pH value, is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, by what is obtained
Sample is dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate, then in H in air atmosphere at 400 DEG C2Atmosphere
In 500 DEG C of reductase 12 h, the catalyst of preparation is labeled as CAT-9.
Embodiment 10
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane：It is the same with the process step of embodiment 1, simply by pretreatment abandoned catalyst in direct synthesis methylchlorosilane
Sintering temperature is changed to 400 DEG C, and acid used replaces with HCl.
The preparation of catalyst：2.08g WCM are placed in the round-bottomed flask of 50mL deionized waters, 60 DEG C of water-bath uniform stirrings
0.5h, by 3.10g Ni (NO3)2·6H2O, 5.09g Mg (NO3)2·6H2O, 1.32g 50wt%Mn (NO3)2It is dissolved separately in
In 50g water, and the KOH solution of 0.2mol/L is configured, then above-mentioned 4 kinds of solution cocurrents are added drop-wise in round-bottomed flask, Deca process
Middle pH meter detects pH value, is controlled 9 or so, and after 60 DEG C of water-bath uniform stirring 8h, filtering and washing to pH is 7 or so, will
The sample for obtaining is dried 12h in 100 DEG C.Gained sample calcines 4h, 2 DEG C/min of heating rate in air atmosphere at 400 DEG C, then
In H2700 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-10.
Catalyst performance evaluation
Normal pressure methanation catalyst reactivity worth is carried out to embodiment 1,2,3,4,5,6,7,8,9,10 and certain commercial catalysts
Test.The catalyst of the mesh of 500mg 20～40 is fitted in crystal reaction tube, H is passed through2(flow velocity：100mL/min) temperature programming
Reduction, 2 DEG C/min of heating rate, the reductase 12 h at 400 DEG C are cooled to afterwards 260 DEG C.Reactor feed gas consist of H2:CO:N2
Volume flow rate ratio is 3:1:1, reaction pressure is normal pressure, and mass space velocity is 30000mLh-1·g-1, reaction temperature：260–550
DEG C, with 20 DEG C of intervals, one point, high-temperature region (400-550 DEG C) are with 50 DEG C of intervals, one point, each temperature for low-temperature space (260-360 DEG C)
Degree point constant temperature 60min or so sampling, with Micro3000 gas chromatograies raw material and gaseous product composition are analyzed.
The active testing result of the catalyst that above-described embodiment and comparative example are prepared in implementing is as shown in the table：
Note：
Wherein：N is the molal quantity of correspondence component
Thus table is visible, the Ni-based methanation catalyst activity of pure abandoned catalyst in direct synthesis methylchlorosilane prepared by comparative example 1 load compared with
Difference, abandoned catalyst in direct synthesis methylchlorosilane is significantly improved via the activity of the modified catalyst obtained afterwards of inorganic oxide, under 550 DEG C of high temperature
Conversion ratio and CH to CO4Selectivity reached the ultimate value of calculation of thermodynamics under the temperature and pressure.With existing side
Method prepare nickel content (20～40wt%) it is higher, while add auxiliary agent catalyst compare (Chinese patent CN1041968A and
CN101468311A), in embodiment 1,2,3,4 prepare nickel oxide content for 20wt% catalyst activity also apparently higher than
Prior art prepares the activity of catalyst.In addition, adding manganese oxide, vanadic anhydride auxiliary agent to significantly improve the low of catalyst
Warm activity, such as 260 DEG C, under normal pressure, conversion ratios of the CO on CAT-6 catalyst can just reach 80%, illustrate catalyst of the present invention
Compared with commercial catalysts, not only with relatively higher high temperature active, while with excellent low temperature active.
To the stability of catalyst CTA-6 obtained in embodiment 6,8 and certain commercial catalysts in pressurization methanation reaction
Tested.The catalyst of the mesh of 500mg 20～40 is fitted in crystal reaction tube, H is passed through2(flow velocity：30mL/min) program liter
Temperature reduction, 2 DEG C/min of heating rate, the reductase 12 hour at 600 DEG C.Reactor feed gas consist of H2：CO：N2Volume flow rate ratio is
3:1:1, reaction pressure is 3.0MPa, and mass space velocity is 30000mLg-1·h-1, reaction temperature is 550 DEG C.We select certain
Commercial catalysts (NiO mass fractions are 45%, with titanium aluminum oxide as carrier) are compared.Note：CH4Yield=(CO conversion ratios
╳CH4Selectivity)/100
Carbon deposition quantity on stability test rear catalyst is detected using carbon and sulfur analytical instrument.
Fig. 4 is the methanation catalyst and certain commercial catalysts of silicon waste catalyst load prepared by embodiment 6,8 in methanation
Catalytic life evaluation result in reaction：CH4Yield with the response time change.From fig. 4 it can be seen that commercial catalysts are anti-
During answering, CH4Yield occur in that obvious downward trend.3.0MPa, after 550 DEG C of reaction 70h, CH4Yield by under 89%
Drop to 78%.Thermal gravimetric analysis results show that the carbon deposition quantity in commercial catalysts reaches 15wt%.React under similarity condition after 70h,
The silicon waste catalyst catalyst of load nickel oxide proposed by the present invention, CH on CAT-6 and CAT-84Conversion ratio it is basicly stable, reaction
Afterwards the carbon deposition quantity on CAT-6 only has 2wt%, and CAT-8 carbon deposition quantities only have 3wt%.Illustrate the catalysis of catalyst proposed by the present invention
Activity, heat stability and anti-carbon performance are superior to selected commercialized catalyst.
As described above, obtained methanation catalyst is compared with selected commercial catalysts are tested in prior art,
The aspects such as catalyst activity, anti-sintering, the anti-carbon performance of abandoned catalyst in direct synthesis methylchlorosilane base catalyst proposed by the present invention all have bright
Aobvious advantage, the catalyst coal or biomass pyrolytic or gasification produce rich in CO and H2Gaseous mixture and industrial coke oven
Have a good application prospect in the methanations such as gas.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (38)
1. a kind of Ni-based methanation catalyst that abandoned catalyst in direct synthesis methylchlorosilane is loaded, the catalyst includes active component, carrier, is modified
Agent and auxiliary agent, wherein, the active component is nickel；Carrier is abandoned catalyst in direct synthesis methylchlorosilane；Modifying agent is porous inorganic oxide, is helped
Agent is transition metal oxide.
2. catalyst as claimed in claim 1, it is characterised in that with the content meter of oxide, the gross mass of catalyst is
100%, each component accounts for the mass percent of catalyst gross mass and is respectively：
Active component 10～70%
Auxiliary agent 0.5～15%
Carrier and modifying agent surplus, modifying agent is 0.05～2 with the mass ratio of carrier.
3. catalyst as claimed in claim 2, it is characterised in that the mass percent of the active component is 10～25%.
4. catalyst as claimed in claim 2, it is characterised in that the mass percent of the active component is 25～60%.
5. catalyst as claimed in claim 4, it is characterised in that the mass percent of the active component is 30～50%.
6. catalyst as claimed in claim 2, it is characterised in that the modifying agent is 0.05～0.3 with the mass ratio of carrier.
7. catalyst as claimed in claim 2, it is characterised in that the modifying agent is 0.25～2 with the mass ratio of carrier.
8. catalyst as claimed in claim 1, it is characterised in that the modifying agent is Al2O3、TiO2、ZrO2, MgO or SiO2
In any one or at least two mixture.
9. catalyst as claimed in claim 1, it is characterised in that the auxiliary agent is V2O5、Cr2O3、CeO2、La2O3Or MnO2In
Any one or at least two mixture.
10. catalyst as claimed in claim 1, it is characterised in that the abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
11. catalyst as claimed in claim 10, it is characterised in that the pretreatment is comprised the following steps：
A abandoned catalyst in direct synthesis methylchlorosilane is calcined 0.5～5h by () at 300～700 DEG C, then crush and screen out particle diameter for 0.5～100 μm
Abandoned catalyst in direct synthesis methylchlorosilane；
B broken and after sieving abandoned catalyst in direct synthesis methylchlorosilane is carried out pickling by (), then filter, be dried, ball milling, and Ball-milling Time is 12～
24h。
12. catalyst as claimed in claim 11, it is characterised in that the acid is H2SO4、HCl、H3PO4、HNO3Or in acetic acid
Any one or at least two mixture.
13. catalyst as claimed in claim 11, it is characterised in that the concentration of the acid is 0.1～4.0mol/L.
14. catalyst as claimed in claim 11, it is characterised in that it is described acid usage amount to make abandoned catalyst in direct synthesis methylchlorosilane in institute
1～3 times of containing metal oxide sour amount needed for being completely dissolved.
15. catalyst as claimed in claim 11, it is characterised in that the number of times of the pickling is at least one times.
16. catalyst as claimed in claim 11, it is characterised in that the pickling time is 2～12h.
17. catalyst as claimed in claim 11, it is characterised in that the baking temperature be 100～200 DEG C, the time be 5～
24h。
A kind of 18. preparation sides of the Ni-based methanation catalyst of the abandoned catalyst in direct synthesis methylchlorosilane load as described in one of claim 1-17
Method, it is characterised in that the method comprising the steps of：
By the raw material needed for synthesizing activity component, auxiliary agent and modifier components, according to the composition of catalyst, cocurrent adds organosilicon
In the dispersion liquid of waste catalyst, while Deca precipitant, and control system pH is 7.5～11, precipitation is made completely, before obtaining catalyst
Liquid solution is driven, is then filtered, washed, be dried, calcined and reduce, obtain the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load
Agent.
19. methods as claimed in claim 18, it is characterised in that the abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
20. methods as claimed in claim 19, it is characterised in that the pretreatment is comprised the following steps：
A abandoned catalyst in direct synthesis methylchlorosilane is calcined 0.5～5h by () at 300～700 DEG C, then crush and screen out particle diameter for 0.5～100 μm
Abandoned catalyst in direct synthesis methylchlorosilane；
B broken and after sieving abandoned catalyst in direct synthesis methylchlorosilane is carried out pickling by (), then filter, be dried, ball milling, and Ball-milling Time is 12～
24h。
21. methods as claimed in claim 20, it is characterised in that the acid is H2SO4、HCl、H3PO4、HNO3Or in acetic acid
Any one or at least two mixture.
22. methods as claimed in claim 20, it is characterised in that the concentration of the acid is 0.1～4.0mol/L.
23. methods as claimed in claim 20, it is characterised in that the usage amount of the acid is contained in abandoned catalyst in direct synthesis methylchlorosilane to make
1～3 times of metal-oxide sour amount needed for being completely dissolved.
24. methods as claimed in claim 20, it is characterised in that the number of times of the pickling is at least one times.
25. methods as claimed in claim 20, it is characterised in that the pickling time is 2～12h.
26. methods as claimed in claim 20, it is characterised in that the baking temperature be 100～200 DEG C, the time be 5～
24h。
27. methods as claimed in claim 18, it is characterised in that the preparation method of the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid is：
Abandoned catalyst in direct synthesis methylchlorosilane is dispersed in water, 40～90 DEG C are heated to, the pH value of precipitant regulation system is then adopted for 7.5
～11, obtain the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane.
28. methods as described in claims 27, it is characterised in that the precipitant is NaOH, KOH, Na2CO3、K2CO3, carbon
In the aqueous solution of sour ammonium and ammonia any one or at least two combination, its concentration be 0.2～2.0mol/L.
29. methods as claimed in claim 18, it is characterised in that needed for synthesizing activity component, auxiliary agent and modifier components
As a solution cocurrent is added in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane raw material.
30. methods as claimed in claim 29, it is characterised in that the raw material needed for synthesis modification agent is selected from aluminum, magnesium, zirconium, titanium
Or the nitrate of silicon, carbonate, chloride, silicate or ester.
31. methods as claimed in claim 29, it is characterised in that the raw material needed for synthesizing activity component is nickel nitrate, sulphuric acid
In nickel, Nickel dichloride. or nickel acetate any one or at least two combination.
32. methods as claimed in claim 29, it is characterised in that the raw material needed for additive synthesis is selected from chromium, manganese, cerium or lanthanum
Nitrate or carbonate, or vanadyl acetylacetonate.
33. methods as described in claim 30 or 32, it is characterised in that the carbonate and chromium of aluminum, magnesium, zirconium or titanium, manganese, cerium
Or the carbonate of lanthanum adds nitric acid to dissolve to form solution when using.
34. methods as described in claim 30 or 32, it is characterised in that the chloride of titanium, ester or vanadyl acetylacetonate are used
When be dissolved in ethanol and form solution.
35. methods as claimed in claim 18, it is characterised in that the Deca raw material under conditions of stirring, mixing time be 3～
10h。
36. methods as claimed in claim 18, it is characterised in that the calcining heat is 400～700 DEG C, and calcination time is 2
～6h.
37. methods as claimed in claim 18, it is characterised in that the reduction temperature is 400～800 DEG C, and the recovery time is 1
～3h.
38. methods as claimed in claim 18, it is characterised in that the method comprising the steps of：
1) pretreatment of abandoned catalyst in direct synthesis methylchlorosilane carrier：
1-1) by abandoned catalyst in direct synthesis methylchlorosilane at 300～700 DEG C, 0.5～5h is calcined, then crush and screen out particle diameter for 0.5～100
μm abandoned catalyst in direct synthesis methylchlorosilane；
1-2) abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out into pickling, then filter, be dried and ball milling, Ball-milling Time is 12
～24h；
2) preparation of catalyst：
2-1) by step 1) in the pretreated abandoned catalyst in direct synthesis methylchlorosilane that obtains be dispersed in water, be heated to 40～90 DEG C, adopt
The pH value of precipitant regulation system is 7.5～11, obtains the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane；
2-2) by the raw material needed for synthesizing activity component, auxiliary agent and modifying agent, according to the composition of catalyst, it is respectively configured to molten
Liquid, cocurrent is added to 2-1) in the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid that obtains, while Deca precipitant, and control system pH value is
7.5-11,3～10h is stirred, obtain catalyst precursor mixed liquor；
2-3) catalyst precursor is filtered, washed and dried, products therefrom calcines 2～6h at 400～700 DEG C, after
At 400～800 DEG C, 1～3h is reduced, form the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
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