CN104248957B - Lighter hydrocarbons steam preconversion catalyst and its preparation method and application - Google Patents
Lighter hydrocarbons steam preconversion catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of light hydrocarbon feedstocks steam preconversion catalyst, with W metal as active component, MgO is carrier to this catalyst, Al2O3For carrier and auxiliary agent, not siliceous and magnesium aluminate spinel.Catalytic component to be calculated with oxide content, containing 26 34 parts of NiO, 49 64 parts of MgO, 9.4 15 parts of Al2O3.It is applied to light hydrocarbon feedstocks steam pre-inversion, in 350 650 DEG C of temperature, steam/hydrocarbons ratio 0.5 4.5mol/mol, carbon space velocity≤6000h‑1, under pressure normal pressure to 4.0MPa process conditions, hydrogen making, ammonia synthesis gas, methyl methanol syngas, oxo-synthesis gas, town gas etc., it is high to have good low temperature conversion activity, intensity, the strong adaptability to raw material and process conditions, C2Above hydrocarbon conversion rate>99%.Using this catalyst, the adaptability of raw material is strengthened, reduce the severity of reburner operation, be conducive to device energy-saving, reduce production cost, and the service life of reforming catalyst can be extended.This method for preparing catalyst and technique for applying are simple, it is easy to accomplish.
Description
Technical field
The invention belongs to hydrocarbon steam conversion technical field is and in particular to a kind of lighter hydrocarbons steam preconversion catalyst and its system
Preparation Method and application.
Background technology
Abroad with French TECHNIP company, Johnson Matthey company of Britain, DenmarkCompany, moral
The companies such as Lurgi, Linde, Uhde of state are the technology suppliers of representative, and hydrocarbon steam conversion technology is persistently studied
And exploitation, obtain greater advance at aspects such as Technology, energy regenerating, catalyst performance and the conversion type of furnaces, so that hydro carbons is steamed
Vapour transformation technology is ripe day by day, and hydrogen supply reliability, motility are increased substantially, and achieves preferable economic benefit.
One distinguishing feature of external hydrocarbon steam conversion technology pre reforming Process that has been commonly used.Urge in hydrocarbon raw material
Change in the technical process that steam converts hydrogen making or synthesis gas, hydrocarbon raw material generally first passes through pre-conversion process, described hydrocarbon
Class raw material such as natural gas, liquefied petroleum gas（LPG）, refinery gas, the hydro carbons such as Petroleum.
Hydrocarbon raw material converts production hydrogen through steam or the dominant response of synthesis gas is as follows：
CnHm+nH2O→nCO+(n+m)H2（1）
CnHm+(2n-m/2)H2→nCH4（2）
CnHmRepresent hydrocarbon raw material component.Gasification and hydrogenation reaction（Reaction equation 1 and 2）It is irreversible and be performed until
Go out reactor.CO shift reaction and methanation reaction（Reaction equation 3 and 4）Be reversible and be up to balance.Total is anti-
Should be：
CnHm+wH2O→eCO+bCO2+cH2+dCH4+eH2O （5）
Other possible reactions also have：
C+H2O→CO+H2（9）
The advantage of pre reforming Process is mainly manifested in：
（1）Strong to adaptability to raw material, from natural gas, casing-head gas, refinery gas to the light oil doing 220 DEG C, these compositions are multiple
Miscellaneous hydrocarbon raw material all can be directly entered the conversion that pre-transform teactor realizes high methane gas, increased reforming unit to raw material
Adaptability, reforming catalyst to steam/hydrocarbons ratio and raw material composition conversion sensitivity reduce, substantially prolongs reforming catalyst and
The life-span of transformation catalyst；
（2）Pre-inversion outlet process gas is high methane gas, with CH4、CO、CO2、H2、H2Based on O, such that it is able to significantly carry
The inlet temperature of high reburner, reburner inlet temperature is improved to 600-650 DEG C by 450-520 DEG C, can make full use of conversion
Furnace flue gas exhaust heat, reduces the outer defeated quantity of steam of reforming unit, reduces thermal loss；
（3）Pre-inversion outlet process gas is practically free of C2Above hydro carbons, improves reburner and steam/hydrocarbons ratio and raw material is formed
Adaptability, it is to avoid the overtemperature of coking and boiler tubes in reformer tube for the higher hydrocarbon materials, eliminate boiler tube occur the torrid zone or
The danger of hot spot；
（4）Apply pre reforming technology to make the senior hydrocarbon reaction originally carrying out in reburner go to reaction condition relatively to relax
Pre-transform teactor in carry out, alleviate the thermic load of reburner, improve reburner reaction condition.
With the development of home and abroad gas chemical industry, petrochemical industry, the design carbon space velocity of pre-transform teactor is increasingly
Height, industrial has at present occurred in that carbon space velocity 5000h-1Above pre-transform teactor, such as middle extra large oil refining Limited Liability
Company Huizhou refines oil the large-scale hydrocarbon steam conversion device that branch company introduces the DAVY company of Johnson Matthey company subordinate
And its supporting catalyst, the carbon space velocity of pre-transform teactor reaches 5300h-1.
Chinese patent ZL99120474.3 discloses a kind of steam preconversion catalyst for hydrocarbon, and this catalyst activity metal is
Nickel, accelerator is the oxide of alkaline-earth metal, and carrier is the mixture of at least two class refractory inorganic oxides, and the first kind is
The kieselguhr of high porosity, Equations of The Second Kind is the aluminium oxide of high intensity, and use ratio is 1：0.1-1：0.8.Evaluating catalyst liquid air
Fast 4.0h-1, equivalent carbon space velocity about 4200h-1.This catalyst is in use it is impossible to tolerate the process conditions more than 540 DEG C；
Catalyst requires it is impossible to meet existing process using carbon space velocity is relatively low；Active component nickel content is high, and catalyst is expensive.
Chinese patent CN200910018512.X discloses a kind of hydro carbons pre-inversion for large-scale energy-saving type hydrogen producing technology
Catalyst, this catalyst with nickel as active constituent, using rare earth metal（Lanthanum and/or cerium）And/or the oxide of alkaline-earth metal is
Auxiliary agent, with the refractory material silicon oxide of synthetic as carrier.The content of active constituent nickel is calculated as 10%-70% with nickel oxide, helps
Agent magnesium oxide accounts for the 0.5%-45% of total catalyst weight, and carrier accounts for the 10%-70% of total catalyst weight, can be reached using carbon space velocity
To 1000-2000h-1.It is applied to natural gas, liquefied petroleum gas（LPG）, refinery gas, the hydrocarbon raw material such as Petroleum.This catalyst
Carbon space velocity relatively low it is impossible to meet the requirement of technological development.
Chinese patent ZL200510043725.X discloses a kind of gaseous hydrocarbon low temperature insulation transformation catalyst and its reaction work
Skill, the active metal of this catalyst is nickel, and carrier is aluminum contained compound, with the oxide of rare earth metal and/or alkaline-earth metal
Oxide is accelerator, is calculated in mass percent, the salic 54%-94% of catalyst, nickel oxide 5%-45%, and rare earth metal aoxidizes
The oxide content 0.1%-15% of thing and/or alkaline-earth metal, using in 350-650 DEG C of reactor inlet temperature, outlet temperature
400-600 DEG C, reaction pressure is normal pressure to 5.0MPa, steam/hydrocarbons ratio 1.5-4.5, carbon space velocity 500-3000h-1.This catalyst makes
With during, C can not be carried in raw natural gas2Or C2Above component, otherwise C quickly2Above higher hydrocarbon penetrates after jeopardizing
Continuous reforming catalyst, thus limiting the type of feed that this catalyst is suitable for, can only be raw material using natural gas, and can not make
Use casing-head gas；In addition, this catalyst using carbon space velocity relatively low it is impossible to meet existing process require.
Chinese patent CN201010244880 discloses a kind of gaseous hydrocarbon, liquid hydrocarbon dual-purpose pre-conversion catalyst and its preparation
Method, with nickel oxide as active component, aluminum calcium composite oxides are accelerator to this catalyst, γ-Al2O3Sedimentation type for carrier
Catalyst, by weight, NiO50-66 part, Al2O316-23 part, CaO2-5 part.Aluminum calcium complexes are aluminium hydroxide, heavy carbonic acid
The complex of calcium.Evaluating catalyst is with oil product for liquid air speed 6.0h during raw material-1, during with gaseous hydrocarbon for raw material, gas air speed 5000h-1.Catalyst requires it is impossible to meet existing process using carbon space velocity is relatively low；Active component nickel content is high, catalyst high cost.
Raise with crude oil price, oil plant deep processing, polish, domestic oil plant was used for hydrogen manufacturing, preparing synthetic gas in the past
Gaseous hydrocarbon resource in containing more C2Or C2Above olefin component, for the consideration of resource utilization and benefit, refinery tends to
In these olefin component being extracted using PSA or deep cooling or other technological means；C4Resource is in the comprehensive utilization of oil plant
Also put into practice；In addition, the demand of civil liquefied gas is also increasingly increasing, C3And C4More as liquefied gas
Ingredient.Thus lead to gaseous hydrocarbon inadequate resource, hydrocarbon steam conversion device needs additionally to supplement a part of liquid hydrocarbon conduct
Raw material, such as light naphthar, raffinate oil, C5Group is graded.Traditional pre-converting catalyst processes gaseous hydrocarbon, the energy of liquid hydrocarbon mixed material
Power is not enough, and for pre-inversion reaction process it is desirable to the activity of catalyst is higher, performance is more excellent, is resistant to higher carbon space velocity
Process conditions, ensure certain service life simultaneously.
Chinese patent application 201110255124.0 belongs to the conventional achievement in research of inventor, using nickel-magnesium-aluminum system,
Account for the 6-25% of total catalyst weight in terms of Ni, the molar ratio of magnalium is 3：1-12：1.This catalyst aims natural gas, liquefaction
Oil gas（LPG）, the gaseous hydrocarbonaceous feedstock steam pre-inversion such as refinery gas, do not account for C during research and development5Or C5More than
Hydrocarbon raw material steam converts.And practical application in industry, often gaseous hydrocarbonaceous feedstock deficiency in enterprise, and supplements part Petroleum
Situation as raw material.When converting such raw material, the process gas of this catalyst often carry partly the C of not conversion completely2Or C2With
Upper component.Because the reforming catalyst that subsequent transformation stove uses does not possess anti-C2Or C2The ability of above component, thus jeopardized turn
Change the service life of catalyst and the safety in production of enterprise.For making up disadvantages mentioned above, inventor optimizes catalyst further
Formula, improves catalyst preparation process, improves the C-C bond dissociation energy power of catalyst and converts activity stabilized during liquid hydrocarbon
Property, form the present invention.
Content of the invention
It is an object of the invention to provide a kind of catalyst of the steam pre-inversion being applied to light hydrocarbon raw material, this catalyst is fitted
Answer process conditions ability strong, can be used for light hydrocarbon raw material pre-inversion hydrogen making, ammonia synthesis gas, methyl methanol syngas, town gas
In technique, adapt to high carbon space velocity≤6000h-1, low temperature conversion activity is good, all applicable under the conditions of inlet temperature 350-650 DEG C,
There is stronger anti-carbon deposition ability simultaneously；Invention also provides the preparation method and application of this catalyst.
Lighter hydrocarbons steam preconversion catalyst of the present invention is nickel-magnesium-aluminum System Catalyst, with W metal as activearm
Point, alkaline earth oxide MgO is carrier, Al2O3For carrier and auxiliary agent.
In the catalyst of the present invention, calculated with oxide weight, the MgO, 9-15 of the NiO containing 26-35 part, 49-64 part
The Al of part2O3.Additionally, in catalyst preparation process, adding lubricant 3-5 part, water 5-15 part.
Lubricant is selected from graphite, paraffin, any one or a few in stearate.
In the present invention, unless otherwise noted, the water of use is deionized water.
The catalyst pores of the present invention divide three types：In the aperture of 5-10nm, quantity at most, accounts for total a kind of pore-size
The 37%-42% of pore volume；A kind of pore-size, in the mesopore of 10-25nm, accounts for the 24%-28% of total hole volume；A kind of pore-size
In the macropore of 100nm or bigger, account for the 20%-24% of total hole volume.
The catalyst specific pore volume of the present invention is in 0.0850-0.0950mL/g.
The method for preparing catalyst of the present invention adopts depositing technology, after the salts solution of nickel, magnesium, aluminum is mutually mixed,
It is added drop-wise under stirring in precipitant and carries out precipitation, completion of dropping continues to stir under ultrasonic assistant, and precipitation is anti-
Successively through aging, washing, dry, the prepared semi-finished product catalyst of kinetics after should terminating；Above-mentioned stirring is all to make in ultrasound wave
With under carry out.
Typically the salts solution of nickel, magnesium, aluminum is mutually mixed, metallic salt typically adopts nitrate or sulfate.
Precipitant typically adopts carbonate, such as sodium carbonate, potassium carbonate, sodium hydroxide etc..For ensureing to precipitate completely, precipitant must have
Amount, in the present invention, controls precipitant excessive 10% or more.
The reaction occurring in precipitation process is briefly described as follows：
Or react as follows：
Ni2++2OH-→Ni(OH)2↓ （13）
Mg2++2OH-→Mg(OH)2↓ （14）
Al3++3OH-→Al(OH)3↓ （15）
The reaction actually occurring is complex, and the precipitate of formation is the double salt of nickel, magnesium, aluminum.
According to the method for the present invention, nickel, magnesium, aluminium compound are to be produced by the acidity of reactant and effect of both alkalescence
Precipitation, thus be to precipitate, precipitate is a kind of fine and close green mixture, and in subsequent preparation process simultaneously
In, remain this densifie state.
Precipitate slurry is preferably prepared in accordance with the following methods, and dress nickel, magnesium, aluminum solutions in container A, in another one container B
Middle dress precipitant, the solution of container A is slowly dropped to container B, maintains certain mixing speed simultaneously.
According to the method for the present invention, nickel, magnesium, the metal ion molar concentration of aluminum mixed aqueous solution are 1.0-4.0mol/L,
Preferably 1.5-2.5mol/L.
According to the method for the present invention, the metal ion molar concentration of precipitant aqueous solution is 0.5-3.0mol/L, preferably
1.0-2.0mol/L.Precipitant aqueous solution be sodium carbonate, potassium carbonate, one or more of sodium hydroxide.
Solution in container A, container B must keep certain temperature, and particularly container B must keep certain temperature,
Be conducive to the uniform precipitate of acquisition state, and the nickel crystallite size of finished catalyst is had a major impact.
According to the method for the present invention, the solution temperature of container A is 45-90 DEG C, preferably 60-80 DEG C；The solution temperature of container B
Spend for 45-90 DEG C, preferably 60-80 DEG C；Slightly higher 2-5 DEG C of the solution temperature container B solution temperature of container A.
According to the method for the present invention, mixing speed controls in 0.20-0.42rad/s, preferably 0.29-0.36rad/s.If stirring
Mix excessive velocities or excessively slow, the nickel crystallite size of sedimentary uniformity and finished catalyst will be affected.
According to the method for the present invention, the speed that nickel, magnesium, aluminum solutions are added drop-wise to precipitant solution should be maintained at 0.1-
0.4mol/min, preferably 0.15-0.25mol/min.If rate of addition is too fast or excessively slow, sedimentary uniformity and finished product are catalyzed
The nickel crystallite size of agent will be affected.
According to the method for the present invention, after the solution of container A is all added drop-wise to container B, stirring should be continued to it is ensured that thing
Material reacts completely, and the time control continuing stirring is in 15-30 minute.
According to the method for the present invention, when agitator works, it is to make precipitation granule tiny as far as possible it is ensured that sedimentary
Uniformity, opens ultrasound wave and serosity is shaken, and assists stirring paddle to improve stirring capacity, pulverizes precipitate so as to trickleer,
Ultrasound wave is closed after agitator stops.
Can be attached by flange between supersonic generator and ultrasound wave distributor, as shown in Fig. 2 ultrasonic wavelength-division
Cloth device is located at reactor bottom.
Ultrasound wave distributor used is arranged on reactor bottom, and the curved surface by reactor bottom dissipates ultrasound wave.Ultrasonic
Wave frequency is higher, and ultrasound wave is easily decayed, and frequency too low noise is too big, and the ultrasound wave being therefore typically chosen 20-50KHz is more suitable
Preferably, the sound intensity is generally 0.4-1W/cm2.
According to the method for the present invention, after the solution of container A is all added drop-wise to container B, question response terminates, and slurry pH value is
Alkaline range, when with sodium carbonate, potassium carbonate for precipitant, slurry pH value is preferably 8-9；When with sodium hydroxide as precipitant
When, slurry pH value is preferably 10-11；PH value controls in this scope it can be ensured that nickel, magnesium, aluminum precipitate completely, it is to avoid the wave of material
Take.
According to the method for the present invention, after the solution of container A is all added drop-wise to container B, the temperature of container B should be maintained at
45-90 DEG C, preferably 60-80 DEG C, preferably identical with temperature during precipitation.
According to the method for the present invention, after the solution of container A is all added drop-wise to container B, maintain certain mixing time it
Afterwards, stop stirring, allow serosity stop motion, the temperature of constant container B, carrying out serosity ageing time is 1-12 hour.
According to the method for the present invention, after the aging end of serosity, immediately filtration washing should be carried out to serosity.In order to avoid serosity is old
Change overlong time, crystal grain is grown up affects catalyst activity too much；Or slurry temperature reduces, detersive efficiency is caused to decline, waste is gone
Ionized water and time.
According to the method for the present invention, the filtration washing of serosity should use deionized water.For the deionized water of washing, Ying Bao
Hold at 45-90 DEG C, preferably 60-80 DEG C, preferably identical with temperature during precipitation.
When filtration washing is carried out to serosity, it is possible to use the mode such as vacuum filtration, plate and frame filter pressing, centrifugal filtration, wherein
The detersive efficiency of plate and frame filter pressing is higher, is preferred version.
Slurry amount is typically 50-600 times of purpose catalyst quality, preferably 80-200 times.When washing is to use
0.1% concentration diphenylamines sulphate reagent titrate for colourless when, that is, think washing reached target, can by filter cake from cross diafiltration
Wash in equipment and take out, filter cake color is light green color, is mainly made up of the double salt of nickel, magnesium, aluminum.
Precipitate scrubbed removal Na+Or K+Afterwards, send into exsiccator, be heated to 120-125 DEG C, be dried, drying time
24-48h；It is then fed into roaster, is heated to 400-500 DEG C, be dehydrated and decompose, constant temperature time controls in 1-6h, preferably
For 2-4h.It is dried and kinetics must separately be carried out, otherwise precipitate will appear from the uneven distribution of material, precipitate ruptures
Face outward appearance has obvious color distortion.
During roasting, catalyst pore structure can automatically tend to stable, and reacts to each other in grain edges, interlocks mixed
Close, hole can be produced further, so that the pore structure of catalyst is flourishing.
Filter cake is referred to as semi-finished product after drying, kinetics, and semi-finished product are dark grey color powder.
Add 3-5 part lubricant in 100 parts of semi-finished product, be placed in mixing and ball milling 10-60 minute in ball grinder, preferably 15-
30 minutes, 90wt.% can be reached above by 120 eye mesh screens through the material of ball milling.
Add the water of 5-15 part, preferably 8-12 part water, mix homogeneously in material after ball milling, roll, pelletize, 95wt.%
Above material can pass through 20 eye mesh screens, compressing.
The pre-converting catalyst of the present invention can be prepared into cylindrical shape or the cellular specially-shaped annular of double sphere seven apertures in the human head, and heap is close
Degree 1.0-1.2g/mL.As cylindrical shape, a diameter of 3.5-6mm, highly for 3.5-6mm, side pressure strength is up to more than 300N/；
The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter is 10-16mm, internal diameter 0.5-2.0mm, hole count 7, highly for 8-11mm, hole
To side pressure strength up to more than 250N/.
Used reducibility gas before catalyst uses, such as hydrogen, NiO is reduced into W metal.Due to urging of the present invention
Agent employs a large amount of MgO as carrier, and Ni crystal grain is separated by MgO, is effectively prevented Ni crystal grain clinkering and grows up, thus extending
In the life-span of catalyst, there is the very high nanoscale nickel crystallite of catalysis activity simultaneously, through the fresh catalyst nickel crystallite of reduction
Less than 22nm.
Catalyst according to method of the present invention preparation does not contain sodium.Thus avoiding hydrocarbon steam conversion course of reaction
In, catalysis activity decline, follow-up heat recovery system or CO shift reaction that the sodium due to containing in catalyst causes
The problem of the top fouling of device, causes heat recovery system heat recovery efficiency to decline, CO shift reaction device upper catalyst
Agent activity decrease.Even if the catalyst of the present invention has sodium, also it is due to preparation technology or raw material in catalyst preparation process
The restriction of purity, is present in catalyst with extremely trace impurity, Na≤0.05wt%.
Catalyst according to method of the present invention preparation does not contain potassium.The catalyst of the present invention has had higher catalysis
Activity, by the MgO existing a large amount of in carrier component, during the normal use of catalyst, will not occur coking deactivation to ask
Topic.Therefore, the catalyst of the present invention does not need just to complete the pre-inversion reaction of light hydrocarbon raw material by the charcoal effect that disappears of potassium
Process, thus avoiding the potassium containing high level in common hydrocarbon vapours catalyst to be used for removing carbon, low temperature conversion is lived
Property relatively low it is impossible to be applied to the defect of high-speed process conditions；Simultaneously, it is to avoid in hydrocarbon steam conversion course of reaction, potassium exists
While removing carbon, it is dissolved in steam from catalyst so that catalyst occurs potassium lost phenomenon, the potassium of loss easily exists again
Dirt is formed at the top of the follow-up heat recovery system of hydrocarbon steam conversion device and CO shift reaction device.The present invention urges
Even if agent has potassium, also it is due to the restriction of preparation technology or material purity in catalyst preparation process, with extremely micro
Impurity is present in catalyst, K≤0.05wt%.
Catalyst according to method of the present invention preparation does not contain silicon.Thus avoid hydrocarbon steam conversion catalyst making
With during common silicon effusion problem, the silicon of loss is again easily in follow-up heat recovery system or CO shift reaction device
Top form dirt.Even if the catalyst of the present invention has silicon, be also in catalyst preparation process using not pure raw material or
Preparation equipment is brought into, is present in catalyst with extremely trace impurity, with SiO2Meter, SiO2≤ 0.1wt%, documents and materials table
Bright, the silicon of such low content will not adversely affect to rear system.
Catalyst according to method of the present invention preparation does not contain ferrum.Even if the catalyst of the present invention has ferrum, also simply exist
Brought into using not pure raw material or Preparation equipment in catalyst preparation process, be present in catalyst with extremely trace impurity,
With Fe2O3Meter, Fe2O3≤0.05wt%.
Catalyst according to method of the present invention preparation does not contain magnesium aluminate spinel.Because temperature during roasting is relatively low, because
This is not in Al2O3React to each other with MgO and combine to form magnesium aluminate spinel.Meanwhile, NiO and MgO mixture is substantially atom
, there is the problem of mutually migration hence without NiO and MgO, that is, be not in nickel magnesium solid solution in the mixture of state.Nickel magnesium melts admittedly
Nickel in body needs very high reduction temperature just can obtain metallic nickel, and the catalyst of the present invention will not produce in preparation process
Nickel magnesium solid solution, so catalyst is very easy to reduction.
The catalyst of the present invention is applied to the process for pretransforming hydrocarbon vapour with lighter hydrocarbons and water vapour as raw material, and pre-inversion is anti-
Device is answered to be cartridge reactor, adiabatic reactor, inlet temperature 350-650 DEG C, outlet temperature 350-650 DEG C, reaction pressure normal pressure is extremely
4.0MPa, the steam/hydrocarbons ratio of reaction controls in 0.5-4.5mol/mol, carbon space velocity≤6000h-1.When for cartridge reactor, can
To fill cylindrical shape or the cellular specially-shaped annular catalyst of double sphere seven apertures in the human head, Fig. 1 is that double cellular specially-shaped annulars of sphere seven apertures in the human head are urged
Agent.
The catalyst of the present invention also can be seated in the reburner catalyst boiler tube of hydrocarbon steam conversion device（Shell and tube is anti-
Answer device）, easily expand production means and a prolongation reforming catalyst use can be provided for old hydrocarbon steam conversion device
The method in life-span is it is recommended that reburner designs carbon space velocity≤800h-1Hydrocarbon steam conversion device use the method, can will convert
Stove carbon space velocity improves to 1100h-1.Recommend the double sphere seven apertures in the human head cellular specially-shaped annular catalyst of filling to reduce boiler tube resistance drop.
In the case, the catalyst of the present invention can be used alone or in combination with reforming catalyst, jointly completes hydrocarbon steam conversion
Reaction, without the single low temperature conversion reactor of setting；When used in combination, the Catalyst packing of the present invention is on boiler tube
The low-temperature space in portion is exactly concretely entrance to 650 DEG C of temperature boiler tube position, phase is then loaded according to process conditions in boiler tube bottom
The reforming catalyst answered.User does not need to adjust the operating parameter of reburner, is continuing with hydrocarbon steam conversion device reburner
Process parameter control device, the common technology parameter of current reburner is：Inlet temperature 480-650 DEG C, exports 750-
950 DEG C, reaction pressure normal pressure to 4.0MPa, reacts steam/hydrocarbons ratio >=1.5mol/mol, carbon space velocity≤1050h-1（Special instruction：It is subject to
The restriction of hydrocarbon steam conversion unit engineering design, leads to carbon space velocity cannot exceed 1050h up till now-1, it is not this catalyst
Restriction lead to carbon space velocity not can exceed that 1050h-1）.
The invention has the advantages that：
The invention provides a kind of light hydrocarbon feedstocks steam preconversion catalyst, this catalyst with W metal as active component,
MgO is carrier, Al2O3For carrier and auxiliary agent, not siliceous and magnesium aluminate spinel, catalytic component to be calculated with oxide content, to contain
The MgO of the NiO of 26-34 part, 49-64 part, the Al of 9.4-15 part2O3.It is applied to light hydrocarbon feedstocks steam pre-inversion, in temperature 350-
650 DEG C, steam/hydrocarbons ratio 0.5-4.5mol/mol, carbon space velocity≤6000h-1, under pressure normal pressure to 4.0MPa process conditions, preparing hydrogen
Gas, ammonia synthesis gas, methyl methanol syngas, oxo-synthesis gas, town gas etc., have good low temperature conversion activity, intensity height, right
Raw material and the strong adaptability of process conditions, C2Above hydrocarbon conversion rate>99%.
Using this catalyst, the adaptability of raw material is strengthened, reduce the severity of reburner operation, be conducive to device section
Can lower consumption, reduce production cost, and the service life of reforming catalyst can be extended.This method for preparing catalyst and technique for applying letter
It is single easy, it is easy to accomplish.
Brief description
Fig. 1 is double sphere seven apertures in the human head cellular special-shaped ring structural representation；
Fig. 1-a is double sphere seven apertures in the human head cellular special-shaped ring front view；
Fig. 1-b is double sphere seven apertures in the human head cellular special-shaped ring top view；
Fig. 2 is the precipitation kettle structural representation that catalyst preparation adopts；
Wherein：1- motor；2- stirring paddle；3- ultrasound probe；4- supersonic generator；5- reactor；6- heating jacket；
Fig. 3 is catalyst preparation flow chart；
Fig. 4 is catalyst pressurization activity rating apparatus structure schematic diagram；
Wherein：1- oil-measuring pump；2- water dosing pump；3- carburator；4- blender；5- tubular reactor；6- condenser；7-
Separator；8- manostat；9- wet flow indicator.
Specific embodiment
With reference to embodiments the present invention is described further.
Activity rating of catalyst method：
Activity rating of catalyst is to be measured on the pressurization activity rating device shown in Fig. 4.
Evaluate raw material：Iso-butane, purity>99.9%, sulfur content<0.5μg/g；No. 6 solvent naphthas, sulfur content<0.5μg/g.
Material rate：Iso-butane：No. 6 solvent naphtha=7：3（mol/mol）, for simulating light hydrocarbon feedstocks.
Catalyst loading amount：60mL.
Process gas are analyzed：Shimadzu GC-8A chromatograph, column length 2m, fill TDX-01,45 DEG C of column temperature, gasify 100 DEG C, detector
100 DEG C, flow velocity 35mL/min.
Table 1,2 is oil product composition analysis data.
No. 16 solvent naphtha race compositions of table
The conventional character of No. 26 solvent naphthas of table
Embodiment 1
Catalyst is prepared as follows：
247g（About 0.85mol）Ni（NO3）2·6H2O, 787g（About 3.07mol）Mg（NO3）2·6H2O, 191g（About
0.51mol）Al（NO3）3·9H2O is soluble in water, is configured to the mixed solution A of 3L, and the metal ion molar concentration of solution A is about
1.48mol/L.
By 547g（About 5.16mol）Na2CO3It is configured to 5L solution B, the metal ion molar concentration of solution B is about
1.03mol/L.
Solution A is warmed up to 75 DEG C, solution B is warmed up to 70 DEG C.
Solution B is placed in reactor, turn on agitator, ultrasound wave, ultrasonic frequency is 50KHz, sound intensity 0.5W/cm2,
Mixing speed controls in 0.30rad/s.With 30 minutes, solution A is added drop-wise in solution B, neutralization precipitation, rate of addition is
100mL/min（I.e. nickel magnesium-aluminum metal ion 0.148mol/min）.
After completion of dropwise addition, it is 50KHz in ultrasonic frequency, sound intensity 0.5W/cm2Under, maintain stirring 15 minutes, use Accurate pH
The pH value measuring serosity is between 8-8.5.
Serosity static aging 2h under 70 DEG C of temperature conditionss.
Using filter washing equipment, serosity is washed, using 70 DEG C of deionized water cyclic washings, filter cake is scrubbed extremely
0.1% concentration diphenylamines sulphate reagent titrate for colourless when it is believed that having reached washing terminal.
After filter cake is dried 24h at 120 DEG C, sends into roaster, be heated to 450 DEG C, carry out dehydration and the decomposition of 4h, constant temperature
4h, that is, obtain semi-finished product.
Take 100g semi-finished product, add 3g graphite, ball milling crosses 120 mesh sieves after 15 minutes.
Take the material after sieving, add 8g H2O, mix homogeneously, rolls, pelletize, crosses 20 mesh sieves.
Take the material after sieving, compressing with forming machine.
Final gained catalyst cylindrical shape, diameter 3.5mm, height 3.5mm, heap density is 1.17g/mL, and side pressure crushes
Intensity 311N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 16mm, internal diameter 2mm, height 10mm, heap density 1.05g/
ML, hole is to side pressure strength 260N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,420 DEG C of inlet temperature, outlet temperature 490
DEG C, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.891 | 15.173 | 14.836 |
| CO,%(v/v) | 0.473 | 0.471 | 0.474 |
| CO2,%(v/v) | 20.684 | 20.557 | 20.637 |
| CH4,%(v/v) | 63.952 | 63.799 | 64.053 |
| C2+,%(v/v) | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon it was demonstrated that this catalyst can be used for converting the prerotation of lighter hydrocarbons
Metallization processes process, process gas composition is stable, C2Content does not measure, and illustrates that catalyst has very high activity and stability.
Measure the nickel crystallite drawing off sample, nickel crystallite 21.6nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 38.9% of pore volume；Pore-size, in the mesopore of 10-25, accounts for the 26.1% of total hole volume；A kind of pore-size is in 100nm or more
Big macropore, accounts for the 21.3% of total hole volume.
Catalyst specific pore volume is in 0.0884mL/g.
After testing in this catalyst, Na≤0.05wt%, K≤0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%.
Embodiment 2
Catalyst is prepared as follows：
247g（About 0.85mol）Ni（NO3）2·6H2O, 787g（About 3.07mol）Mg（NO3）2·6H2O, 191g（About
0.51mol）Al（NO3）3·9H2O is soluble in water, is configured to the mixed solution A of 3L.By 713g（About 5.16mol）K2CO3It is configured to
5L solution B.
Preparation process is with embodiment 1.Sediment slurry Accurate pH measures pH value between 8.5-9.0.
Final gained catalyst cylindrical shape, diameter 5.0mm, height 5.0mm, heap density is 1.18g/mL, and side pressure crushes
Intensity 309N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 12mm, internal diameter 1.0mm, height 11mm, density 1.09g/
ML, hole is to side pressure strength 267N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,420 DEG C of inlet temperature, outlet temperature 490
DEG C, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.812 | 14.995 | 14.827 |
| CO,%(v/v) | 0.477 | 0.471 | 0.474 |
| CO2,%(v/v) | 20.586 | 20.645 | 20.726 |
| CH4,%(v/v) | 64.125 | 63.889 | 63.973 |
| C2+,%(v/v) | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon it was demonstrated that this catalyst can be used for converting the prerotation of lighter hydrocarbons
Metallization processes process, process gas composition is stable, C2Content does not measure, and illustrates that catalyst has very high activity and stability.
Measure the nickel crystallite drawing off sample, nickel crystallite 21.1nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 39.9% of pore volume；Pore-size, in the mesopore of 10-25nm, accounts for the 24.9% of total hole volume；A kind of pore-size in 100nm or
Bigger macropore, accounts for the 22.4% of total hole volume.
Catalyst specific pore volume is in 0.0901mL/g.
After testing in this catalyst, Na≤0.05wt%, K≤0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%.
Embodiment 3
Catalyst is prepared as follows：
247g（About 0.85mol）Ni（NO3）2·6H2O, 787g（About 3.07mol）Mg（NO3）2·6H2O, 191g（About
0.51mol）Al（NO3）3·9H2O is soluble in water, is configured to the mixed solution A of 3L.By 413g（About 10.32mol）NaOH prepares
Become 5L solution B.
Preparation process is with embodiment 1.Sediment slurry Accurate pH measures pH value between 10-11.
Final gained catalyst cylindrical shape, diameter 6.0mm, height 6.0mm, heap density is 1.13g/mL, and side pressure crushes
Intensity 321N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 10mm, internal diameter 0.5mm, height 8mm, heap density 1.04g/
ML, hole is to side pressure strength 265N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,420 DEG C of inlet temperature, outlet temperature 490
DEG C, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.722 | 15.003 | 15.009 |
| CO,%(v/v) | 0.481 | 0.475 | 0.484 |
| CO2,%(v/v) | 20.794 | 20.663 | 20.716 |
| CH4,%(v/v) | 64.003 | 63.859 | 63.791 |
| C2+,%(v/v) | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon it was demonstrated that this catalyst can be used for converting the prerotation of lighter hydrocarbons
Metallization processes process, process gas composition is stable, C2Content does not measure, and illustrates that catalyst has very high activity and stability.
Measure the nickel crystallite drawing off sample, nickel crystallite 21.5nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 41.1% of pore volume；Pore-size, in the mesopore of 10-25nm, accounts for the 26.7% of total hole volume；A kind of pore-size in 100nm or
Bigger macropore, accounts for the 22.3% of total hole volume.
Catalyst specific pore volume is in 0.0914mL/g.
After testing in this catalyst, Na≤0.05wt%, K≤0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%.
Embodiment 4
Catalyst is prepared as follows：
266.8g（About 0.92mol）Ni（NO3）2·6H2O, 787.5g（About 3.08mol）Mg（NO3）2·6H2O,
161.8g（About 0.43mol）Al（NO3）3·9H2O, mixing, soluble in water, it is configured to the mixed solution A of 2L, the metal of solution A
Ion molar concentration is about 2.21mol/L.
By 705.8g（About 5.33mol）K2CO3It is configured to 3L solution B, the metal ion molar concentration of solution B is about
1.70mol/L.
Solution A is warmed up to 78 DEG C, solution B is warmed up to 75 DEG C.
Solution B is placed in reactor, turn on agitator, ultrasound wave, ultrasonic frequency is 20KHz, sound intensity 1W/cm2, stir
Mix speed controlling in 0.40rad/s.With 20 minutes, solution A is added drop-wise in solution B, neutralization precipitation, rate of addition is
100mL/min（I.e. nickel magnesium-aluminum metal ion 0.221mol/min）.
After completion of dropwise addition, it is 20KHz in ultrasonic frequency, sound intensity 1W/cm2Under, maintain stirring 30 minutes, use accurate pH meter
The pH value surveying serosity is between 8-8.5.
Serosity static aging 6h under 75 DEG C of temperature conditionss.
Using filter washing equipment, serosity is washed, using 75 DEG C of deionized water cyclic washings, filter cake is scrubbed extremely
0.1% concentration diphenylamines sulphate reagent titrate for colourless when it is believed that having reached washing terminal.
After filter cake is dried 24h at 125 DEG C, sends into roaster, be heated to 425 DEG C, carry out dehydration and the decomposition of 3h, constant temperature
3h, that is, obtain semi-finished product.
Take 100g semi-finished product, add 5g graphite, ball milling crosses 120 mesh sieves after 30 minutes.
Take the material after sieving, add 12g H2O, mix homogeneously, rolls, pelletize, crosses 20 mesh sieves.
Take the material after sieving, compressing with forming machine.
Final gained catalyst cylindrical shape, diameter 6.0mm, height 6.0mm, heap density is 1.16g/mL, and side pressure crushes
Intensity 309N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 10mm, internal diameter 0.5mm, height 8mm, heap density 1.07g/
ML, hole is to side pressure strength 270N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,450 DEG C of inlet temperature, outlet temperature 480
DEG C, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.748 | 14.911 | 14.675 |
| CO,%(v/v) | 0.477 | 0.483 | 0.473 |
| CO2,%(v/v) | 20.716 | 20.652 | 20.689 |
| CH4,%(v/v) | 64.059 | 63.954 | 64.163 |
| C2+,%(v/v) | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon it was demonstrated that this catalyst can be used for converting the prerotation of lighter hydrocarbons
Metallization processes process, process gas composition is stable, C2Content does not measure, and illustrates that catalyst has very high activity and stability.
Measure the nickel crystallite drawing off sample, nickel crystallite 20.1nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 38.5% of pore volume；Pore-size, in the mesopore of 10-25nm, accounts for the 27.3% of total hole volume；A kind of pore-size in 100nm or
Bigger macropore, accounts for the 23.9% of total hole volume.
Catalyst specific pore volume is in 0.0948mL/g.
After testing in this catalyst, Na≤0.05wt%, K≤0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%.
Embodiment 5
Catalyst is prepared as follows：
207.5g（About 0.72mol）Ni（NO3）2·6H2O, 863.7g（About 3.37mol）Mg（NO3）2·6H2O,
161.8g（About 0.43mol）Al（NO3）3·9H2O, mixing, soluble in water, it is configured to the mixed solution A of 2.5L, the gold of solution A
Belong to ion molar concentration and be about 1.81mol/L.
By 416.9g（About 10.41mol）NaOH is configured to 5.5L solution B, and the metal ion molar concentration of solution B is about
1.89mol/L.
Solution A is warmed up to 65 DEG C, solution B is warmed up to 60 DEG C.
Solution B is placed in reactor, turn on agitator, ultrasound wave, ultrasonic frequency is 50KHz, sound intensity 0.4W/cm2,
Mixing speed controls in 0.33rad/s.With 40 minutes, solution A is added drop-wise in solution B, neutralization precipitation, rate of addition is
62.5mL/min（I.e. nickel magnesium-aluminum metal ion 0.113mol/min）.
After completion of dropwise addition, it is 50KHz in ultrasonic frequency, sound intensity 0.4W/cm2Under, maintain stirring 30 minutes, use Accurate pH
The pH value measuring serosity is between 10-10.5.
Serosity static aging 12h under 60 DEG C of temperature conditionss.
Using filter washing equipment, serosity is washed, using 65 DEG C of deionized water cyclic washings, filter cake is scrubbed extremely
0.1% concentration diphenylamines sulphate reagent titrate for colourless when it is believed that having reached washing terminal.
After filter cake is dried 48h at 120 DEG C, sends into roaster, be heated to 490 DEG C, carry out 1.5h dehydration and decomposition, constant temperature
3h, that is, obtain semi-finished product.
Take 100g semi-finished product, add 4g graphite, ball milling crosses 120 mesh sieves after 20 minutes.
Take the material after sieving, add 10g H2O, mix homogeneously, rolls, pelletize, crosses 20 mesh sieves.
Take the material after sieving, compressing with forming machine.
Final gained catalyst cylindrical shape, diameter 4.5mm, height 5.0mm, heap density is 1.20g/mL, and side pressure crushes
Intensity 341N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 14mm, internal diameter 1.4mm, height 10mm, heap density 1.17g/
ML, hole is to side pressure strength 290N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,450 DEG C of inlet temperature, outlet temperature 480
DEG C, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.748 | 14.911 | 14.883 |
| CO,%(v/v) | 0.475 | 0.482 | 0.474 |
| CO2,%(v/v) | 20.719 | 20.654 | 20.781 |
| CH4,%(v/v) | 64.058 | 63.953 | 63.862 |
| C2+,%(v/v) | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon it was demonstrated that this catalyst can be used for converting the prerotation of lighter hydrocarbons
Metallization processes process, process gas composition is stable, C2Content does not measure, and illustrates that catalyst has very high activity and stability.
Measure the nickel crystallite drawing off sample, nickel crystallite 20.6nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 41.9% of pore volume；Pore-size, in the mesopore of 10-25nm, accounts for the 24.2% of total hole volume；A kind of pore-size in 100nm or
Bigger macropore, accounts for the 23.2% of total hole volume.
The catalyst specific pore volume of the present invention is in 0.0858mL/g.
After testing in this catalyst, Na≤0.05wt%, K≤0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%.
Embodiment 6
Carry out process conditions simulation in the present embodiment, done experiment with the catalyst of embodiment 2.
Experimental condition：It is passed through iso-butane, No. 6 solvent naphthas and water and carry out steam reforming reaction, pressure 3.0MPa, carbon space velocity
6000h-1, steam/hydrocarbons ratio 2.0,350 DEG C of inlet temperature, 650 DEG C of outlet temperature, evaluation time 500h.Dry gas composition is as follows：
| Test period/h | 100 | 200 | 300 | 400 | 500 |
| H2,%(v/v) | 38.384 | 38.344 | 38.365 | 38.457 | 38.46 |
| CO,%(v/v) | 3.737 | 3.731 | 3.735 | 3.739 | 3.733 |
| CO2,%(v/v) | 19.263 | 19.194 | 19.313 | 19.091 | 19.182 |
| CH4,%(v/v) | 38.616 | 38.731 | 38.587 | 38.713 | 38.625 |
| C2+,%(v/v) | - | - | - | - | - |
After off-test, catalyst granules is complete, does not tie carbon, C in process gas2Or C2Above hydro carbons, explanation
Catalyst has high activity.It is applicable that this catalyst is used for lighter hydrocarbons steam pre reforming Process, can be filled in and turn
Change stove boiler tube top low-temperature space.
Comparative example 1
Embodiment C- by the catalyst of embodiment 3, embodiment A-6, ZL99120474.3 of ZL200510043725.X
1st, the catalyst of C-2 is contrasted.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,420 DEG C of inlet temperature, outlet temperature 490
DEG C, evaluation time 100h.Dry gas composition is as follows：
After off-test, draw off catalyst it is seen that ZL200510043725.X catalyst overlying catalyst is pulverized, outward appearance has
Significantly powdered carbon；All there is powdered carbon in the middle of ZL99120474C-1, C-2 catalyst inlet-bed.This test shows 4 kinds of catalyst
Performance difference.
Comparative example 2
Pre-converting catalyst, during commercial Application, is generally used in pre-transform teactor, with the conversion in reburner
Catalyst cooperates.After application pre-converting catalyst, the process gas composition entering reburner is mainly CH4、CO、
CO2、H2O, without worrying that higher hydrocarbons thermal cracking is coking, reforming catalyst can use highly active natural gas reforming catalyst,
The carbon space velocity of reburner can bring up to 1200-1400h-1（Retrieve commercial conversion stove design carbon space velocity maximum 1050h at present-1, have no the reburner commercial Application report of higher carbon space velocity）, be conducive to enterprise to reduce hydrogen or synthesis gas production cost.As
Pre-converting catalyst, it is necessary to assure C in pre-transform teactor outlet process gas2Or C2Above component hydrocarbon content refers to less than control
Mark, usually requires to be less than 0.5%（v/v）, in order to avoid form the safety in production of coking impact device in reburner entrance.
Chinese patent application 201110255124.0 belongs to the conventional achievement in research of inventor, is entered with the present invention by test
Row contrast, experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1, steam/hydrocarbons ratio 2.0,430 DEG C of inlet temperature, outlet temperature 495
℃.
201110255124.0 embodiment A-4500 hour evaluation result table
5500 hours evaluation result tables of the embodiment of the present invention
From evaluation result as can be seen that the catalyst performance stabilised of the present invention, outlet process gas is all the time without C2Or C2More than
Component.And 201110255124.0 catalyst is not suitable for converting liquid hydrocarbon steam, this research and development original intention with this catalyst ---
For natural gas, liquefied petroleum gas（LPG）, the gaseous hydrocarbonaceous feedstock steam pre-inversion such as refinery gas develop relevant.
Comparative example 3
Prepare catalyst according to embodiment 5, but do not use ultrasound wave.
Final gained catalyst cylindrical shape, diameter 4.5mm, height 5.0mm, heap density is 1.20g/mL, and side pressure crushes
Intensity 335N/；The cellular specially-shaped annular of double sphere seven apertures in the human head, external diameter 14mm, internal diameter 1.4mm, height 10mm, heap density 1.17g/
ML, hole is to side pressure strength 286N/.
Catalyst breakage, sieve, take the granule between 10-20 mesh, be loaded in the tubular reactor of internal diameter 20mm, urge
Agent loadings 60mL.Carry out external heat with electric furnace, after catalyst hydrogen reducing, be passed through iso-butane, No. 6 solvent naphthas and water and enter
Row steam reforming reaction, with the performance of test catalyst.
Experimental condition：Pressure 3.0MPa, carbon space velocity 6000h-1,
Steam/hydrocarbons ratio 2.0,450 DEG C of inlet temperature, 480 DEG C of outlet temperature, evaluation time 100h.Dry gas composition is as follows：
| Test period/h | 10 | 50 | 100 |
| H2,%(v/v) | 14.732 | 14.897 | 14.857 |
| CO,%(v/v) | 0.477 | 0.481 | 0.472 |
| CO2,%(v/v) | 20.725 | 20.649 | 20.748 |
| CH4,%(v/v) | 64.066 | 63.973 | 63.912 |
| C2+,%(v/v) | - | - | 0.011 |
After off-test, catalyst granules is complete, not broken；In test latter stage process gas composition, a small amount of C occurs2.
Measure the nickel crystallite drawing off sample, nickel crystallite 23.5nm with X-ray diffraction method.
Combine measurement catalyst pore structure with mercury injection method and nitrogen adsorption methods, pore-size, in the aperture of 5-10nm, accounts for total
The 35.6% of pore volume；Pore-size, in the mesopore of 10-25nm, accounts for the 26.9% of total hole volume；A kind of pore-size in 100nm or
Bigger macropore, accounts for the 24.1% of total hole volume.
The catalyst specific pore volume of the present invention is in 0.0849mL/g.
Illustrate that the difference of preparation method can affect catalyst performance.
Comparative example 4
Had considerable document report it is believed that silicon has unstability at high temperature, there is silicon migration phenomenon it is easy to
In follow-up equipment（As waste heat boiler）Low temperature at deposition, fouling, reduce follow-up equipment exchange capability of heat.
The C-1 sample of ZL99120474.3 is tested on thermobalance.Weigh a certain amount of C-1 sample, circulation
Medium is nitrogen and vapor, in 800 DEG C of constant temperature 1h, mass loss can be detected.Chemical analyses are carried out to sample after test,
Silicone content in sample decreases 2%.
The Samples EXAMPLE 13 taking the present invention is tested under similarity condition, can't detect mass loss.
Claims (6)
1. a kind of preparation method of lighter hydrocarbons steam preconversion catalyst it is characterised in that：This catalyst is urged for nickel-magnesium-aluminum system
Agent, with W metal as active component, alkaline earth oxide MgO is carrier, Al2O3For carrier and auxiliary agent；In this catalyst,
Calculated with oxide weight, the MgO of the NiO containing 26-35 part, 49-64 part, the Al of 9-15 part2O3, Na≤0.05wt%, K≤
0.05wt.%, SiO2≤ 0.1wt%, Fe2O3≤0.05wt%；
Described preparation method be the salts solution of nickel, magnesium, aluminum is mutually mixed after, be added drop-wise to precipitant under stirring
In carry out precipitation, completion of dropping continues to stir under ultrasonic assistant, precipitation terminate after successively through aging, washing,
It is dried, kinetics are obtained semi-finished product catalyst；Above-mentioned stirring is all carried out under ul-trasonic irradiation；Ultrasonic frequency is
20-50KHz, the sound intensity is not more than 0.4-1W/cm2；
Described is aging：Ageing time is 1-12 hour；
Described washing：Using deionized water, wash temperature is 45-90 DEG C, and slurry amount is the 50-600 of catalyst quality
Times；Wash to 0.1% concentration diphenylamines sulphate reagent titrate for colourless when, washing terminates；
Described drying：Precipitate is heated to 120-125 DEG C be dried, drying time 24-48h；
Described dehydration, decomposition：Precipitate is heated to 400-500 DEG C, carries out kinetics, the time is 1-6h.
2. lighter hydrocarbons steam preconversion catalyst according to claim 1 preparation method it is characterised in that：Precipitant adopts
Carbonate or alkali, the metal ion molar concentration of precipitant aqueous solution is 0.5-3.0mol/L.
3. lighter hydrocarbons steam preconversion catalyst according to claim 1 preparation method it is characterised in that：Nickel, magnesium, aluminum
Salts solution is nitrate, the aqueous solution of sulfate, oxalates or acetate, and the molar concentration of its metal ion is 1.0-
4.0mol/L.
4. lighter hydrocarbons steam preconversion catalyst according to claim 1 preparation method it is characterised in that：Nickel, magnesium, aluminum
The temperature of salts solution is 45-90 DEG C, and the temperature of precipitant aqueous solution is 45-90 DEG C；Nickel, magnesium, the salts solution of aluminum
Temperature is higher than the temperature of precipitant aqueous solution 2-5 DEG C；Rate of addition 0.1-0.4mol/min, completion of dropping continues auxiliary in ultrasound wave
Help lower stirring, mixing time controls in 15-30 minute, prepared serosity；Mixing speed controls in 0.20-0.42rad/s.
5. lighter hydrocarbons steam preconversion catalyst according to claim 1 preparation method it is characterised in that：By be obtained half
Finished catalyst, in terms of 100 parts by weight, adds 3-5 part lubricant, is placed in mixing and ball milling 10-60 minute in ball grinder, pass through
The material of ball milling can reach 90wt.% above by 120 eye mesh screens；The water of 5-15 part, mixing is added in material after ball milling
Uniformly, roll, pelletize, material can pass through 20 eye mesh screens, compressing；Lubricant is in graphite, paraffin or stearate
One or more.
6. the preparation method according to the arbitrary described lighter hydrocarbons steam preconversion catalyst of claim 1-5 it is characterised in that：
This catalyst is the cellular specially-shaped annular of cylindrical or double sphere seven apertures in the human heads, heap density 1.0-1.2g/mL；
When this catalyst is cylindrical, a diameter of 3.5-6mm, highly for 3.5-6mm, side pressure strength reaches more than 300N/；
When this catalyst is double sphere seven apertures in the human head cellular specially-shaped annular, external diameter is 10-16mm, internal diameter 0.5-2.0mm, hole count 7,
It is highly 8-11mm, hole reaches more than 250N/ to side pressure strength；
This catalyst pores divides three types：
（1）Pore-size, in the aperture of 5-10nm, accounts for the 37%-42% of total hole volume；
（2）Pore-size, in the mesopore of 10-25nm, accounts for the 24%-28% of total hole volume；
（3）Pore-size, in the macropore of 100nm or more than 100nm, accounts for the 20%-24% of total hole volume；
This catalyst specific pore volume is in 0.0850-0.0950mL/g.
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| CN101574658A (en) * | 2009-06-10 | 2009-11-11 | 桂林理工大学 | Method for synthesizing nanometer nickeliferous ternary houghite compound catalyst |
| US20110002831A1 (en) * | 2007-12-14 | 2011-01-06 | Nanning Joerg Arfsten | Sol-gel process with an encapsulated catalyst |
| CN102949994A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | High-activity steam pre-conversion catalyst for hydrocarbons |
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| US20110002831A1 (en) * | 2007-12-14 | 2011-01-06 | Nanning Joerg Arfsten | Sol-gel process with an encapsulated catalyst |
| CN101574658A (en) * | 2009-06-10 | 2009-11-11 | 桂林理工大学 | Method for synthesizing nanometer nickeliferous ternary houghite compound catalyst |
| CN102949994A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | High-activity steam pre-conversion catalyst for hydrocarbons |
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