CN106497619A - A kind of method that Raney alloy catalyst is applied to synthesis gas preparing natural gas by methanation - Google Patents
A kind of method that Raney alloy catalyst is applied to synthesis gas preparing natural gas by methanation Download PDFInfo
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Abstract
The invention provides a kind of method of synthesis gas preparing natural gas by methanation, the method includes for synthesis gas and catalyst carrying out haptoreaction, it is characterized in that, the catalyst includes continuous phase carbon and dispersion phase Raney alloy, wherein, the continuous phase carbon be by one or more can the Organic substance of carbonization obtain after carbonization.When carrying out synthesis gas preparing natural gas by methanation using the method that the present invention is provided, in synthesis gas, the conversion ratio of oxycarbide is higher, even if also, under higher space velocities, the conversion ratio of oxycarbide still is able to reach more than 97%.
Description
Technical field
The present invention relates to a kind of field of synthesis gas preparing natural gas by methanation, more specifically using a kind of thunder Buddhist nun
The method that alloy catalyst carries out synthesis gas preparing natural gas by methanation.
Background technology
In energy-consuming big country, the proportion highest of coal in China's total energy consumption reaches for 2013
66%, this numeral 2007 is 71.1%, declines within continuous 6 years, is still 3 times of global average level,
And the proportion of natural gas is minimum, only account for the 5.8% of total amount, continuous more than 10 years proportion rises, but still with day
45% pole of proportion that right gas is consumed in world energy sources consumption structure does not correspond.Due to producing after combustion of natural gas
Greenhouse gases there was only the 1/2 of coal, the 2/3 of oil, the destructiveness caused by environment less than coal and
Oil, in face of the increasingly severe national conditions of environmental problem, encourages to use natural gas, improves natural gas and exist
Proportion in energy-consuming, becomes only way.
The characteristics of oil lean gas few based on the self-produced energy richness coal of China, the clean applications of coal how are realized, from
And the discharge of the pollutant such as minimizing city coal waste, optimized utilizing energy is realized, national economy is had
There is far-reaching influence.
Synthesis gas is obtained as raw material through coal gasification with coal, synthesis gas obtains synthesis of natural through methanation again
Gas (SNG) route was paid much attention in nearly 5 years, had attracted substantial amounts of investment.
Methanation process and catalyst occupy very important status, methanation in SNG commercial Applications
The research of catalyst lasts for a long time, as the temperature of SNG has attracted the attention of scientific research circle in recent years again
Power.
CN101844080A discloses a kind of catalyst for preparing methane by synthetic gas and preparation method thereof.
It is characterized in that in catalyst preparation process, using carbamide or NH4HCO3Heat resolve generate ammonia with
CO2, on the one hand complex can be formed with catalyst activity component nickel salt, the on the other hand life of a large amount of gases
Into the dispersion for exacerbating granule, porous surface is formed easily, strengthen catalyst activity.
CN103055874A discloses a kind of methanation catalyst, and catalyst preparation step is by containing magnesium
Water soluble salt is attached to Al2O3On, roasting makes catalyst support surface generate magnesia-alumina spinel structure；
The water soluble salt of nickel, magnesium and/or calcium, lanthanide series metal is impregnated on carrier；Dry, roasting, obtains final product and urges
Agent.However, the catalyst is only applicable to the high-load CO hydrogenation processes of 5-40 volumes %, model is suitable for
It is with limit.
CN102319574A discloses a kind of synthesis gas methanation catalyst, is with nickel oxide as activearm
Point, the modified mesopore gama-alumina of cerium oxide is carrier, and transition metal iridium, lanthanum, copper, ferrum or alkaline earth are golden
Category magnesium, the oxide of calcium are auxiliary agent.The preparation method of its mesopore gama-alumina is to adopt hydrothermal synthesis method,
Prepared by the dipping process that nickel-base catalyst is adopted.
Synthesis gas methanation catalyst in addition to the requirement to activity, can also will quickly be derived synthesis gas and be turned
Change the amount of heat of generation in methane reaction processed, it is to avoid hot-spot cause Raney nickel aggregation of particles and
The inactivation that carbon distribution is caused, above patent are also intended to thus, adopt vehicle treated, active component nickel and carrier
Combination, improves the features such as antiwear property is strong, activity is high, carbon accumulation resisting ability is strong, and hyperpyrexia is also described
Inactivation is the common problem of the catalyst.
However, the inorganic oxide carrier metal supported catalyst prepared using infusion process more than above patent,
Need repeatedly to impregnate, repeated calcination, process are complicated, the load capacity of metal be difficult more than 40 weight % (with
Overall catalyst weight be 100% meter), and due to preparation process in high-temperature roasting cause considerable metal
Granule is sintered so that the utilization rate of active metal is relatively low, thus catalyst activity is relatively low.Other are using altogether
Although mixed method or coprecipitation can obtain the catalyst of high metal content, as a large amount of metals are by non-live
Property component parcel, the utilization ratio of metal is very low, and the activity for thus resulting in catalyst is very low.
In catalytic field, " Lei Nifa " is a kind of preparation method of active metal catalyst, the method
It is first to prepare the above alloy of the binary containing active metal, then by least one METAL EXTRACTION out, remains
Under the metal with loose structure there is higher catalytic activity.This method also referred to as " is activated ".Example
Such as, Raney's nickel catalyst (the Industrial and Engineering for being invented by U.S. M.Raney earliest
Chemistry, 1940, Vol.32,1199), which first prepares nickel alumin(i)um alloy, is then dissolved by strong base solution
Aluminium element in alloy, remaining nickel metal have loose structure, with very high catalysis activity, activity
Position more disperses, with higher anti-carbon deposit and hydrothermal stability.
Patent CN1557918 discloses a kind of molding Raney's nickel catalyst and preparation method thereof, the catalysis
Agent be by aluminum and Ni, Co, Cu, Fe in one or more component alloy powder, using intending thin water aluminum
The inorganic matters such as stone as binding agent, using the naturally occurring or synthetic Organic substance such as sesbania powder, carboxymethyl cellulose
Matter as duct template, directly kneadings, molding, roasting, and, institute prepared through caustic solution activation
Obtain catalyst and there is certain shape and intensity, can serve as fixed bde catalyst.But the catalyst preparation
Process is complicated, needs roasting under 900 DEG C of high temperature, high-temperature roasting to cause considerable granule sintering, make
The utilization rate for obtaining active metal is relatively low.
The process that Lei Nifa prepares catalyst is simple, and cost is relatively low, and the catalyst for obtaining has very high activity；
And due to oxide-free auxiliary agent in catalyst, surface is without notable acid or alkaline, anti-carbon performance
Good, catalytic reaction selectivity is good, good stability, therefore prepares a kind of activity by thunder Buddhist nun method high, stable
The good catalyst of property has application prospect for synthesis gas methanation.
Content of the invention
The invention aims to it is natural to overcome the method using existing preparing natural gas by methanation to carry out
When gas is produced, the low defect of the conversion ratio of oxycarbide, there is provided one kind is carried out using Raney alloy catalyst
The method of synthesis gas preparing natural gas by methanation, so that improve the conversion of oxycarbide in production process of natural gas
Rate.
To achieve these goals, the invention provides a kind of method of synthesis gas preparing natural gas by methanation,
The method includes for synthesis gas and catalyst carrying out haptoreaction, it is characterised in that the catalyst includes
Continuous phase carbon and dispersion phase Raney alloy, wherein, the continuous phase carbon is can carbonization by one or more
Organic substance is obtained after carbonization.
When carrying out synthesis gas preparing natural gas by methanation using the method that the present invention is provided, oxidation of coal in synthesis gas
The conversion ratio of thing is higher, even if also, under higher space velocities, the conversion ratio of oxycarbide is remained to
More than 97% is enough reached.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment that states is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of synthesis gas preparing natural gas by methanation, the method is included synthesis gas
Haptoreaction is carried out with catalyst, it is characterised in that the catalyst includes continuous phase carbon and dispersion phase thunder
Damping alloy, wherein, the continuous phase carbon be by one or more can the Organic substance of carbonization obtain after carbonization.
According to the present invention, the haptoreaction can be commonly used in the art for methanation reaction
Carry out in equipment, for example, it is possible to carry out in fixed bed, moving bed or fluid bed, preferably fixed bed.
In the present invention, to catalytic condition, there is no particular limitation, can routinely make for this area
Suitable for the reaction condition of methanation, for example, reaction condition can include：Reaction temperature is
200-800 DEG C, preferably 250-650 DEG C；Reaction pressure is 0-6MPa, preferably 1-3MPa；Raw material
Gas air speed is 5000-30000h-1, preferably 8000-20000h-1, more elect 8000-15000h as-1.
The pressure that the present invention is used is gauge pressure, and air speed is volume space velocity.
According to the present invention, there is no particular limitation to the unstripped gas for methanation reaction for the present invention, can be with
For the unstripped gas for methanation reaction commonly used in the art, in the preferred case, it is possible to use close
Into gas, the synthesis gas is obtained through coal gasification with coal as raw material, it is preferable that in the synthesis gas,
The content of oxycarbide is 3-30%.
According to the present invention, can carbonization Organic substance through carbonization after so that Raney alloy is dispersed in continuous phase carbon
In, and with continuous phase carbon strong bonded, as continuous phase carbon itself has loose structure so that catalyst
There is very high intensity.In a preferred embodiment, the present invention by can carbonization Organic substance and thunder
Carbonization is carried out after damping alloy mixing, the complex of carbon and Raney alloy is obtained, Raney alloy is to carbonisation
Facilitation is played, carbonization can be made to carry out more complete, after carbonization, Raney alloy is dispersed in continuously
In phase carbon, and with continuous phase carbon strong bonded, continuous phase carbon itself has loose structure so that compound urge
Agent has very high intensity.Meanwhile, Raney alloy is dispersed in the space of carbon, and solution or gas can be with
Raney alloy is easily touched, is so conducive to next soaking catalyst with alkaline solution
When, Raney alloy can be easier to be activated the high activity Raney metal to form porous, while a small amount of nothing
Sizing carbon is also washed away, and continuous state material is able to reaming, and more Raney metals are exposed, so as to
Improve the activity of catalyst.
In the present invention, there is no particular limitation for condition of the present invention to the carbonization, for example, the carbon
Changing can be carried out in tubular heater, and carburizing temperature is 500-1800 DEG C, preferably 600-950 DEG C；
Carbonization time is 1-10h, preferably 2-5h.
In the present invention, in situations where it is preferred, the carbonization can be carried out under an inert atmosphere, this
It is bright that to the inert atmosphere, there is no particular limitation, as long as inert environments can be provided, for example, can
To carry out under inert gas conditions.Preferably, the noble gases can be nitrogen and/or argon.
According to the present invention, the Raney alloy can include Raney metal and the element that can be leached.Wherein,
The Raney metal refers to insoluble metal when being activated with Lei Nifa；The element being leached refers to uses thunder
The element that Buddhist nun's method can be dissolved when activating.The present invention is not special to the content of Raney metal in catalyst
Limit, for example, on the basis of the gross weight of catalyst, the content of the Raney metal can be 10-90
Weight %, preferably 20-70 weight %, more preferably 30-60 weight %, provided in the present invention
In preferred embodiment, the content of Raney metal can be 40-50 weight %.
According to the present invention, the present invention contains to Raney metal in the Raney alloy and the element that can be leached
There is no particular limitation for amount, can be content commonly used in the art, for example, in the Raney alloy
In, Raney metal is 1 with the weight ratio of the element that can be leached:99-10:1, preferably 1:10-4:1.
In the present invention, in the preferred case, Raney alloy can be graininess, and its mean diameter can be with
As 0.1-1000 μm, preferably 10-100 μm.
According to the present invention, the Raney metal can be at least one in nickel, cobalt, copper and ferrum, preferably
For nickel or cobalt；The element being leached can be at least one in aluminum, zinc and silicon, preferably aluminum.
According to the present invention, can carbonization Organic substance refer to process under certain temperature, atmospheric condition organic
Thing, hydrogen, oxygen, nitrogen, sulfur in Organic substance etc. are completely or partially vapored away, so as to obtain a kind of phosphorus content
Very high synthetic material, obtained material with carbon element have the property such as high temperature resistant, high intensity, high-moduluss, porous
Energy.The present invention to can the Organic substance of carbonization there is no particular limitation, for example, it is possible to be organic polymer material
At least one in material is preferably plastics and/or its modified plastics, more preferably thermosetting plastics.This
To the plastics, there is no particular limitation for invention, can be various plastics commonly used in the art, for example,
Polyolefin, poly(4-methyl-1-pentene), polyamide can be selected from (such as nylon -5, PA-12, Buddhist nun
Dragon -6/6, nylon-6/10, nylon-11), polycarbonate resin, homopolymerization and/or copolymerized methanal, saturation two
(aromatic ring macromolecule divides by linear polyester, aromatic ring macromolecule obtained in polycondensation reaction for first acid and dihydroxylic alcohols
The polymer that is only made up of aromatic ring and linking group of son, such as polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone (PAS),
Poly aryl ketone.Aromatic polyester, aromatic polyamides), (heterocyclic polymer is on molecular backbone to heterocyclic polymer
Also have the macromolecular material of heterocycle, such as polybenzimidazoles in addition to aromatic ring), fluoropolymer, acrylic acid seriess
In resin, mephenesin Carbamate, epoxy resin, phenolic resin, Lauxite and melamine resin
At least one.Preferably, the plastics can be selected from vistanex, polyamide, polystyrene,
At least one in epoxy resin and phenolic resin, more preferably polypropylene, nylon-6, nylon -66, polyphenyl
At least one in ethylene, phenolic resin and epoxy resin.
In the present invention, the modified plastics refers to the modified product obtained using existing modifying plastics method
Thing.Under preferable case, modifying plastics method can be：Polarity or non-polar monomer or its polymer connect
Branch is modified, by with inorganic or organic reinforcing, toughening material, once just material, increase thermostability material
The melt blending of the materials such as material is modified.
In the present invention, in a preferred embodiment, the catalyst can be according to following steps
It is prepared：
(1) suitable curing system is configured to according to the conventional curing formula of thermoset macromolecule material,
And mix homogeneously；
(2) any of particle size needed for fixed bde catalyst or fluid catalyst can met
Raney alloy powder is initially charged in the mould of cavity shape, adds the curing system obtained by step (1),
Then Raney alloy powder is added, and partially cured sizing is carried out under conventional condition of cure, then to portion
The pelleted substrate for being coated with Raney alloy powder of point solidifying and setting passes through conventional use of organic polymer
Material processing plant proceeds molded curing, obtains catalyst precarsor；
(3) catalyst precarsor that will be obtained by step (2) carbon under inert gas shielding, hot conditionss
Change, that is, obtain non-activated catalyst；
(4) the non-activated catalyst obtained using alkaline solution activation step (3).
In step (1), the curing system can be liquid system, pulverized solid system or granule
Shape solid-state system, wherein, liquid system directly can stir；Pulverized solid system directly can be blended
Even；After granulated solid system can be crushed with industrial conventional any disintegrating apparatus, blending is uniform.
In step (3), the condition of the carbonization is as it was previously stated, here is omitted.
In step (4), the alkaline solution is inorganic alkali solution commonly used in the art, excellent
In the case of choosing, can be NaOH or KOH, preferably NaOH, also, the alkaline solution
Concentration can be 0.5-30 weight %, preferably 10-25 weight %；The condition of the activation includes：
The temperature of activation is 25-95 DEG C；The time of activation is 5min-72h, preferably 1-30h.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
A, by polyglycol distearate (goodization chemistry, PEG400MS) 80g, firming agent methyl four
Hydrogen phthalic anhydride (MeTHPA) (the Guangdong flourishing age reaches science and trade limited company) 68g, three ethanol of curing accelerator
Amine (TEA) (Tianjin Chemical Reagents Factory No.1) 1.2g stirs.
B, the curing system prepared in 50g steps (1) is weighed, dripped in having been added to portion with dropper
In the cylindrical die of point Nickel Aluminium Alloy Powder, in nickel alumin(i)um alloy, nickel content is 48 weight %, aluminium content 52
Weight %, then mould is filled up with Nickel Aluminium Alloy Powder, compression molding instrument is put into, in 120 DEG C of temperature, pressure
30min is molded under conditions of power 7MPa, granule is taken out, is placed among nickel alumin(i)um alloy powder body, uses flat board
Vulcameter is molded 90min under conditions of 150 DEG C of temperature, pressure 7MPa, takes out cooling, sieves,
Cylindrical particle is sifted out, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, obtain catalyst precarsor, claimed
Weight is 160g；
C, 100mL catalyst precarsors are measured, carbonization in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate,
600 DEG C of furnace temperature, is kept for 3 hours, and nitrogen is protected, and flow is 200mL/min；
D, deionized water configuration 20%NaOH aqueous solution 400mL, add step c gained unactivated
Catalyst 50mL, 85 DEG C of keeping temperature filters out solution after 4 hours, that is, obtain the load for activating
Type catalyst A1, in final catalyst, nickel content of metal is about 40 weight %, washs to close neutrality
Afterwards, deposit in standby in deionized water.
(2) synthesis gas methanation reaction performance test
Measure 5mL catalyst A1 and load rustless steel fixed bed reactors, be passed through high pure nitrogen, flow
For 300mL/min, 120 DEG C are warming up to, high pure nitrogen are switched to hydrogen then, be warming up to 450 DEG C,
The synthesis gas of incision, reaction pressure are 3.0MPa, and after reaction, gas composition uses gas chromatographic analysiss.
As a result as shown in table 1.
Volume % of each component in synthesis gas：CO 6%, CO23%, H231%, CH460%.
Embodiment 2
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
A, liquid-state epoxy resin (Ba Ling petrochemical industry, CYD-128) and firming agent hexamethylenetetramine are used
Homogenizer is sufficiently mixed, and hexamethylenetetramine is 12 with liquid-state epoxy resin weight ratio：100；Will
100 grams of compounds are sufficiently mixed with homogenizer with 300 grams of Nickel Aluminium Alloy Powders, nickel in Nickel Aluminium Alloy Powder
Content be 48 weight %, 52 weight % of aluminium content；
B, tablet machine is warming up to 90 DEG C, above material is put in mould and is molded on tablet machine,
It is shaped to the thick sheet materials of 2mm；Tablet machine is warming up to 150 DEG C, the sheet material of forming is placed again into
Solidify 10min in mould on the tablet machine under the pressure of 5MPa；
C, the 2mm thick sheets being cured are cut into little particle, that is, obtain non-activated catalyst precarsor；
D, 100mL little particles are measured, carbonization in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate,
650 DEG C of furnace temperature, is kept for 3 hours, and nitrogen is protected, and flow is 200mL/min；
E, deionized water configuration 20%NaOH aqueous solution 400g, before adding step d gained catalyst
Body 50mL, 85 DEG C of keeping temperature filter out solution after 4 hours, that is, obtain the supported catalyst for activating
Agent A2, in final catalyst, nickel content of metal is about 40% (weight), after washing to close neutrality,
Deposit in standby in deionized water.
(2) synthesis gas methanation reaction performance test
Measure 5mL catalyst A2 and load rustless steel fixed bed reactors, be passed through high pure nitrogen, flow
For 300mL/min, 120 DEG C are warming up to, high pure nitrogen are switched to hydrogen then, be warming up to 450 DEG C,
The synthesis gas of incision, reaction pressure are 3.0MPa, and after reaction, gas composition uses gas chromatographic analysiss.
As a result as shown in table 1.
Volume % of each component in synthesis gas：CO 6%, CO23%, H231%, CH460%.
Embodiment 3
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
A, by polyglycol distearate (goodization chemistry, PEG400MS) 80g, firming agent methyl four
Hydrogen phthalic anhydride (MeTHPA) (the Guangdong flourishing age reaches science and trade limited company) 68g, three ethanol of curing accelerator
Amine (TEA) (Tianjin Chemical Reagents Factory No.1) 1.2g stirs.
B, the curing system prepared in 50g steps (1) is weighed, dripped in having been added to portion with dropper
In the cylindrical die of point Nickel Aluminium Alloy Powder, in nickel alumin(i)um alloy, nickel content is 48 weight %, aluminium content 52
Weight %, then mould is filled up with Nickel Aluminium Alloy Powder, compression molding instrument is put into, in 120 DEG C of temperature, pressure
30min is molded under conditions of power 7MPa, granule is taken out, is placed among nickel alumin(i)um alloy powder body, uses flat board
Vulcameter is molded 90min under conditions of 150 DEG C of temperature, pressure 7MPa, takes out cooling, sieves,
Cylindrical particle is sifted out, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, obtain catalyst precarsor, claimed
Weight is 180g；
C, 100mL catalyst precarsors are measured, carbonization in tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate,
800 DEG C of furnace temperature, is kept for 3 hours, and nitrogen is protected, and flow is 200mL/min；
D, deionized water configuration 20%NaOH aqueous solution 400mL, add step c gained unactivated
Catalyst 50mL, 85 DEG C of keeping temperature filters out solution after 4 hours, that is, obtain the load for activating
Type catalyst A3, in final catalyst, nickel content of metal is about 50 weight %, washs to close neutrality
Afterwards, deposit in standby in deionized water.
(2) synthesis gas methanation reaction performance test
Measure 5mL catalyst A3 and load rustless steel fixed bed reactors, be passed through high pure nitrogen, flow
For 300mL/min, 120 DEG C are warming up to, high pure nitrogen are switched to hydrogen then, be warming up to 450 DEG C,
The synthesis gas of incision, reaction pressure are 3.0MPa, and after reaction, gas composition uses gas chromatographic analysiss.
As a result as shown in table 1.
Each group partial volume % in synthesis gas：CO 6%, CO23%, H231%, CH460%.
Embodiment 4
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, wherein, except that in step c,
950 DEG C of furnace temperature, is kept for 2 hours, and argon is protected.Prepared catalyst A4.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst A4.As a result as shown in table 1.
Embodiment 5
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, wherein, except that in step c,
600 DEG C of furnace temperature, is kept for 5 hours, and nitrogen is protected.Prepared catalyst A5.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst A5.As a result as shown in table 1.
Embodiment 6
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, catalyst A6 is obtained.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst A6, reaction temperature is 270 DEG C, and reaction pressure is
3MPa.As a result as shown in table 1.
Embodiment 7
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, catalyst A7 is obtained.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst A7, reaction temperature is 650 DEG C, and reaction pressure is
3MPa.As a result as shown in table 1.
Embodiment 8
The method that the present embodiment is used for the synthesis gas preparing natural gas by methanation that present invention offer is described.
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, catalyst A8 is obtained.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst A8, volume % of each component in synthesis gas：CO
15%, CO26%, H269%, CH410%.As a result as shown in table 1.
Comparative example 1
(1) preparation of catalyst
Preparation method is with reference to CN103055874A, the nickel gold for preparing alumina load by infusion process
Metal catalyst, the catalyst contain 40 weight % nickel metals.Prepared catalyst D1.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst D1.As a result as shown in table 1.
Comparative example 2
(1) preparation of catalyst
Catalyst is prepared using method same as Example 1, wherein, except that in catalyst
The carbonisation of step c is not carried out in preparation process, and catalyst D2 is obtained.
(2) synthesis gas methanation reaction performance test
Synthesis gas methanation reaction performance test, wherein, institute are carried out using method same as Example 1
Except for the difference that methanation reaction is carried out using catalyst D2.As a result as shown in table 1.
Table 1
Note：Oxycarbide (COx) conversion ratio be participate in reaction COx and unstripped gas COx mole
Than.
According to the result of table 1, by embodiment 1-8 is compared with the result of comparative example 1-2,
When carrying out synthesis gas preparing natural gas by methanation using the method that the present invention is provided, oxycarbide in synthesis gas
Conversion ratio is higher, even if also, (such as 15000h under higher space velocities-1), oxycarbide turn
Rate still is able to reach more than 97%.
In addition, by embodiment 6 and 7, carrying out synthesis gas methane using the method that the present invention is provided
When changing preparing natural gas, under the conditions of the reaction temperature of relatively low (such as 270 DEG C), the conversion ratio of oxycarbide
It still is able to reach more than 90%, under the conditions of the reaction temperature of higher (such as 650 DEG C), although oxycarbide
Conversion ratio limited by Thermodynamics, but its conversion ratio still can reach more than 70%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition that wants, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method of synthesis gas preparing natural gas by methanation, the method are included synthesis gas and catalyst
Carry out haptoreaction, it is characterised in that the catalyst includes continuous phase carbon and dispersion phase Raney alloy,
Wherein, the continuous phase carbon be by one or more can the Organic substance of carbonization obtain after carbonization.
2. method according to claim 2, wherein, the catalytic condition includes：Institute
Stating haptoreaction is carried out in fixed bed, moving bed or fluid bed, preferably fixed bed；Reaction temperature is
200-800 DEG C, preferably 250-650 DEG C；Reaction pressure is 0-6MPa, preferably 1-3MPa；Raw material
Gas air speed is 5000-30000h-1, preferably 8000-20000h-1.
3. method according to claim 1 and 2, wherein, in the synthesis gas, oxidation of coal
The volume content of thing is 3-30%.
4. method according to claim 1, wherein, the condition of the carbonization includes：Carbonization temperature
Spend for 500-1800 DEG C, preferably 600-950 DEG C；Carbonization time is 1-10h, preferably 2-5h；Institute
Stating carbonization is carried out under an inert atmosphere.
5. method according to claim 4, wherein, the inert atmosphere is carried by nitrogen or argon
For.
6. method according to claim 1, wherein, the Raney alloy comprising Raney metal and
The element that can be leached.
7. method according to claim 6, wherein, on the basis of the gross weight of catalyst, institute
The content for stating Raney metal is 10-90 weight %, preferably 20-70 weight %, and more preferably 30-60 is again
Amount %.
8. method according to claim 6, wherein, the Raney metal is in nickel, copper and ferrum
At least one, preferably nickel；The element being leached is at least one in aluminum, zinc and silicon,
Preferably aluminum.
9. the method according to any one in claim 6-8, wherein, in the Raney alloy
In, Raney metal is 1 with the weight ratio of the element that can be leached:99-10:1, preferably 1:10-4:1.
10. method according to claim 1, wherein, described can the Organic substance of carbonization be organic high
At least one in molecular material, preferably plastics and/or its modified plastics, more preferably thermosetting plastics.
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| CN103566976A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method thereof |
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| CN104511314A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Low-temperature methanation catalyst and preparation method thereof |
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| CN103566976A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method thereof |
| CN104511314A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Low-temperature methanation catalyst and preparation method thereof |
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