CN105709794A - Hetero-type methanation catalyst and molding process and application thereof - Google Patents
Hetero-type methanation catalyst and molding process and application thereof Download PDFInfo
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- CN105709794A CN105709794A CN201410719909.2A CN201410719909A CN105709794A CN 105709794 A CN105709794 A CN 105709794A CN 201410719909 A CN201410719909 A CN 201410719909A CN 105709794 A CN105709794 A CN 105709794A
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Abstract
The present invention discloses a hetero-type methanation catalyst and a molding process and application thereof. The process is as follows: nickel-based synthesis gas methanation catalyst powder is prepared into porous cylinder particles by compression or squeezing, wherein diameter Phi of a profile circumscribed circle of the porous cylinder particles is 3-22mm, height is 3-12mm, ratio of surface area / grain skeleton volume is 0.8-1. 6mm<2> / mm<3>, the maximum radial mass transfer distance is 1.4-4.0mm, and the geometric shape of the porous cylinder particles is regular and symmetrical. The molding process of the hetero-type methanation catalyst aims at process characteristics and requirements of various stages of the synthesis gas methanation process, the utilization efficiency of catalyst active components can be improved, and the hetero-type methanation catalyst has an important role for reducing bed resistance drop and improving long-time operational stability of the catalyst.
Description
Technical field
The present invention relates to a kind of synthesis gas methanation catalyst, particularly relate to a kind of special-shaped methanation catalyst and moulding process thereof and application.
Background technology
In recent years, due to the increase of the rising of China's natural gas consumption figure and supply demand gap, cause that Gas Prices rises steadily, by coal through synthesis gas (CO+H2) methanation produces the process of substitute natural gas (SubstituteNaturalGas, SNG) and be subject to again industry and extensively pay attention to, it is believed that it is one of important means alleviating China's natural gas disparities between supply and demand.The dominant response that synthesis gas produces the generation of SNG technical process by methanation reaction is as follows:
CO+3H2→CH4+H2O△H0=-206kJ/mol (1)
2CO+2H2→CH4+CO2△H0=-247kJ/mol (2)
CO2+4H2→CH4+2H2O△H0=-165kJ/mol (3)
Reaction (1) and (2) is the methanation of CO in synthesis gas, is called a large amount of methanation (BulkMethanation), belongs to strong exothermal reaction.Due to CO content higher (being generally about 20vol% in the synthesis gas that such as Lurgi gasifier produces) in reacting gas, and the CO often converting 1vol% can produce the adiabatic temperature rise of 72 DEG C, therefore methanation generally adopts the mode of multistage and gas circulation to control reaction bed temperature in a large number, therefore gas circulating compressor becomes the dynamic equipment of the requisite key of coal to SNG process, and its power consumption also becomes weighs the important technology index that coal to SNG technical process is good and bad.Recycle compressor power consumption is closely related with methanator beds resistance drop, and traditional spherical or cylindrical catalyst particle layers is that tight type piles up filling, and the resistance drop of beds is bigger；And adopt the bed with fillings such as abnormally-structured catalyst such as porous cylindrical, porous gear-like, porous honeycomb, porous sphericals, its bed voidage can improve more than 20%, bed resistance drops and can effectively reduce, thus reducing the regular job power consumption of recycle compressor in a large amount of methanations.Additionally, a large amount of methanation reaction temperature are generally more than 600 DEG C, the surface temperature of catalyst is then higher, and under too high reaction temperature, longtime running will make catalyst activity component particle agglomeration, carrier sinter.Therefore, except the high-temperature stability setting about raising catalyst from catalyst component formulation, adopt abnormally-structured catalyst granules also to be able to promptly transmission and discharge catalytic inner duct and the reaction heat of catalyst surface generation, thus keeping high temperature active and the stability of catalyst.According to disclosed document announcement, a large amount of methanation technology employing of Davy company of Britain having coal to SNG methanation patented technology at present is four hole plum blossom-shaped catalyst, and what Topsoe company of Denmark then adopted is seven apertures in the human head cylindrical catalyst.Energy group in one's power of domestic each colleges and universities, Research Center also develops numerous high temperature full methanation catalyst, such as CN200910187675.0, CN201010223996.4, CN201010127840.6, CN201110351012.5, CN201110336259.X etc., but mainly all concentrate on the invention of formula and synthetic method, be substantially free of the information relating to catalyst configuration aspect.
Abnormally-structured methanation catalyst equally also can give CO2Methanation reaction, namely reaction (3) brings benefit, and this reaction is called supplementary methanation (TrimMethanation), and its effect is on the basis of a large amount of methanation of CO, by the CO in reaction system2Generation CH it is hydrogenated with further with a small amount of CO4, to meet the prescription of SNG product.In the multi-section circulation technique of synthesis gas SNG, owing to the methanation load of this segment process is little, therefore this reaction mainly in, low-temperature space (250-450 DEG C) occurs.Mainly emphasize that high-temperature stability is different from a large amount of methanation catalyst of CO, CO2Supplementary methanation catalyst mainly emphatically be the high activity under middle low temperature so that CO2Hydro-conversion as much as possible.It is currently used for the CO of synthesis gas SNG2Methanation catalyst patent, such as patent CN201010034230.1, CN200910117686.1 etc., still focuses principally on and realizes its invention from catalyst formulation and synthetic method.It is true that from kinetics angle, CO2Methanation be internal diffusion be the course of reaction of rate-determining steps, therefore, for catalysagen granule, it is provided that more granule surface area/volume ratio and less axial, radial mass transfer distance, the effect improving unit grain catalyst volume catalytic active component utilization rate can be played equally.
In sum, for the synthesis gas methanation in coal to SNG technique, for a large amount of methanation of CO and CO2Supplementing methanation feature, a kind of special-shaped methanation catalyst moulding process of development is significant.
Summary of the invention
It is an object of the invention to provide a kind of special-shaped methanation catalyst moulding process application in synthesis gas methanation reaction.Compared with traditional spherical or cylindrical catalyst granule, adopt special-shaped methanation catalyst granule provided by the invention in synthesis gas methanation SNG process, it is possible to for a large amount of methanation of CO and CO2Supplement process characteristic and the requirement of methanation, play effect of catalyst to greatest extent, the utilization ratio of active component in catalyst granules can not only be improved, and reduction beds resistance drop, raising long-lasting catalytic operation stability are had very important important function.For achieving the above object, the technical solution used in the present invention is as follows:
A kind of special-shaped methanation catalyst, this catalyst is the porous cylinder beaded catalyst of the regular symmetry of geometry that Ni-based synthesis gas methanation catalyst powder body is made by the mode of tabletting or extrusion, this porous cylinder beaded catalyst profile circumscribed circle diameter is Φ 3-22mm, height 3-12mm, and surface area/grain skeleton volume ratio is 0.8-1.6mm2/mm3, radially maximum mass transfer distance is 1.4-4.0mm, and side pressure strength is 80-200N/cm.
Described Ni-based methanation catalyst powder body adopts the synthesis technique of chemical coprecipitation, precipitation from homogeneous solution or high-temperature water thermal synthesis to prepare, and in described Ni-based methanation catalyst, the weight percentage of NiO is 40-60%.The described preferred profile circumscribed circle diameter of porous cylinder beaded catalyst be Φ 8-22mm, height 5-10mm, this porous cylinder beaded catalyst preferred surface long-pending/grain skeleton volume ratio is 0.8-1.3mm2/mm3, radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is 120-200N/cm.
Described Ni-based methanation catalyst powder body adopts the technique such as infusion process, beating method to prepare, and in Ni-based methanation catalyst, the weight percentage of NiO is 20-30%.Described porous cylinder beaded catalyst is preferably Φ 3-14mm, highly 5-10mm, the surface area/grain skeleton volume ratio of this porous cylinder beaded catalyst is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is 80-140N/cm.
The moulding process of a kind of special-shaped methanation catalyst, carries out according to following steps:
Insert in wet type batch mixer after the particle diameter Ni-based synthesis gas methanation catalyst powder body less than 0.15mm is mixed with graphite, is the HNO of 3% by mass concentration continuously when material powder body rotates3Aqueous solution is vaporific be injected to mixed powder surface, continuous wet mixed 60 minutes after whole liquid spray into；
Above-mentioned Ni-based synthesis gas methanation catalyst powder body is made by the mode of tabletting or extrusion the porous cylinder beaded catalyst of the regular symmetry of geometry, this porous cylinder beaded catalyst profile circumscribed circle diameter is Φ 3-22mm, height 3-12mm, and the surface area of this porous cylinder beaded catalyst/grain skeleton volume ratio is 0.8-1.6mm2/mm3, radially maximum mass transfer distance is 1.4-4.0mm, and side pressure strength is 80-200N/cm；
Described catalyst, graphite and HNO3Weight ratio be 100:2-3:40-60.
The porous cylinder beaded catalyst of the regular symmetry of geometry is made in described Ni-based methanation catalyst powder body molding by tabletting mode, and porous cylinder beaded catalyst configuration adopts the cylinder axis exterior surface such as porous gear column, porous petal column to have the form of ditch or groove.The preferred profile circumscribed circle diameter of porous cylinder beaded catalyst be Φ 8-22mm, height 5-10mm, this porous cylinder beaded catalyst preferred surface long-pending/grain skeleton volume ratio is 0.8-1.3mm2/mm3, radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is 120-200N/cm
Described Ni-based methanation catalyst powder body molding adopts the mode of extrusion to make the porous cylinder beaded catalyst of the regular symmetry of geometry.Porous cylinder beaded catalyst is preferably Φ 3-14mm, highly 5-10mm, the surface area/grain skeleton volume ratio of this porous cylinder beaded catalyst is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is 80-140N/cm.
A kind of application of special-shaped methanation catalyst, the porous cylinder beaded catalyst of the regular symmetry of above-mentioned geometry is applied to synthesis gas methanation and produces each operation stage of SNG process, and the application conditions of this porous cylinder beaded catalyst is: pressure is 1.0-5.0MPa, temperature is 250-700 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be 0.80-1.05.
Profile circumscribed circle diameter is Φ 8-22mm, highly 5-10mm, surface area/grain skeleton volume ratio is 0.8-1.3mm2/mm3Radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is that the application conditions of the porous cylinder beaded catalyst of the regular symmetry of geometry of 120-200N/cm is preferred for synthesis gas methanation and produces CO a large amount of methanation stage of SNG process: pressure is 1.0-5.0MPa, temperature is 280-700 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be the CO+CO in 1.00-1.05, raw material of synthetic gas gas2Contents on dry basis be 8-25vol%.
Profile circumscribed circle diameter is Φ 3-14mm, highly 5-10mm, surface area/grain skeleton volume ratio is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is that the application conditions of the porous cylinder beaded catalyst of the regular symmetry of geometry of 80-140N/cm is preferred for synthesis gas methanation and produces the CO of SNG process2Supplement the methanation stage: pressure is 1.0-5.0MPa, temperature is 250-450 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be the CO+CO in 0.80-1.00, raw material of synthetic gas gas2Contents on dry basis be 3-8vol%.
In some of the present invention preferably in embodiment, for ensureing, in the pyroreaction stage of a large amount of methanation of CO, there is sufficiently high activity and hydrothermal stability, Ni-based methanation catalyst powder body adopts chemical coprecipitation, prepared by the synthesis technique of precipitation from homogeneous solution or high-temperature water thermal synthesis, and in Ni-based methanation catalyst the weight percentage of NiO preferably between 40-60%.
In the other preferably embodiment of the present invention, for ensureing that catalyst has relatively low bed resistance in CO a large amount of methanation stage and drops and higher high-temperature-resistant gas scouring capability, Ni-based methanation catalyst powder body molding should adopt the mode of tabletting, porous cylinder beaded catalyst configuration that the cylinder axis exterior surface such as porous gear column, porous petal column should be adopted to have the form of ditch or groove.
In some of the present invention preferably in embodiment, for ensureing at CO2The supplementary methanation reaction stage has good low temperature active, and Ni-based methanation catalyst powder body adopts the technique such as infusion process, beating method to prepare.Based on same reason, in the other preferably embodiment of the present invention, Ni-based methanation catalyst powder body molding should adopt the mode of extrusion.Additionally, due at supplementary methanation stage, CO in process gas2The methanation load of (comprising a small amount of CO) is little, considers from the angle of Technological Economy, and in the other preferably embodiment of the present invention, in Ni-based methanation catalyst, the weight percentage of NiO is preferably between 20-30%.
The invention have the advantages that
Abnormally-structured methanation catalyst has higher granule surface area/skeleton volume ratio and less radial mass transfer distance, produces in SNG technique for synthesis gas full methanation, it is possible to for a large amount of methanation of CO and CO2Supplement process characteristic and the requirement of methanation, play effect of methanation catalyst to greatest extent:
(1) in a large amount of methanation process of CO, can effectively reduce beds resistance drop thus reducing gas circulating compressor power consumption, it is possible to removal methanation reaction heat is thus improving methanation catalyst long-play stability under high-temperature water thermal environment rapidly；
(2) at CO2Supplement in methanation process, it is possible to increase effective catalyst activity surface, reduce inside diffusional resistance, improve the utilization ratio of active component in catalyst granules, and then improve the activity of catalyst；
(3) for a large amount of methanation of CO and CO2Supplement process characteristic and the requirement of methanation, adopt the methanation catalyst of different size, various configuration and NiO content, meet the Technological Economy requirement of coal to SNG methanation process process, catalyst cost and regular job expense can be saved further.
Accompanying drawing explanation
Fig. 1 is embodiment 1 cross sectional dimensions schematic diagram,
Fig. 2 is embodiment 2 cross sectional dimensions schematic diagram,
Fig. 3 is embodiment 3 cross sectional dimensions schematic diagram,
Fig. 4 is embodiment 4 cross sectional dimensions schematic diagram,
Fig. 5 is embodiment 5 cross sectional dimensions schematic diagram,
Fig. 6 is embodiment 6 cross sectional dimensions schematic diagram.
Detailed description of the invention
Below by way of particular specific embodiment, embodiments of the present invention being described, person of ordinary skill in the field can by other features of the content understanding present invention disclosed in the present specification and advantage.The present invention is implemented also by other different specific embodiments or is applied, and the every details in this specification also based on different viewpoints and application, can carry out various amendment and change under without departing from the spirit.
Unless otherwise noted, all numerals occurred in specification and claims of the present invention, for instance the percentage by weight of component, particle scale and some physical parameter value describing granule configuration all should be understood that " about " value.The exact numerical occurred in specification and claims of the present invention should be understood that the section Example constituting the present invention.Although trying hard to be the accuracy ensureing numerical value in the example that the present invention provides, but due to the standard deviation of various measurement technology, the numerical value that any measurement obtains all being inevitably present certain error.
Unless otherwise noted,
Term " profile circumscribed circle diameter " means the circumscribed circle diameter of the symmetrical column type particle cross section of geometry.
Term " surface area/grain skeleton volume ratio " means the surface area (including the surface area of external surface area and endoporus) of all exposures of abnormally-structured granule and the ratio of grain skeleton volume.
Term " radially maximum mass transfer distance " means the radius of the maximum inscribed circle that can obtain on the column type particle cross section that geometry is symmetrical.
Unless otherwise noted, the formula of Ni-based methanation catalyst powder body involved in the present invention and preparation method, such as chemical coprecipitation, precipitation from homogeneous solution, high-temperature water thermal synthesis, infusion process and beating method etc., it is known by researcher in this field.Those skilled in the art all can obtain the methanation catalyst powder body of various NiO content involved in the present invention through the experiment of limited number of time, and therefore the formula of above-mentioned Ni-based methanation catalyst powder body and synthesis technique be not within the scope of protection of the invention.
Embodiment 1:
Insert in wet type batch mixer after particle diameter methanation catalyst powder body 1kg and the 22g graphite that NiO weight percentage is 55% less than 0.15mm is mixed, is the HNO of 3% by 400ml mass concentration continuously when material powder body rotates3Aqueous solution is vaporific be injected to mixed powder surface, continuous wet mixed 60 minutes after whole liquid spray into.It is the cylindrical particles catalyst of uniform 5 Φ 4mm through holes on Φ 18mm, height 10mm, cross section that the mixed powder wet feed obtained makes profile outside diameter with tablet machine after granulator granulation.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 0.82mm2/mm3, radially maximum mass transfer distance is 2.62mm, and side pressure strength is 154N/cm.Being labeled as embodiment 1, its cross-sectional structure size is shown in Fig. 1.The methanation catalyst of above-described embodiment 1 being applied to synthesis gas methanation and produces CO a large amount of methanation stage of SNG process, operating condition is: pressure is 3.0MPa, temperature is 650 DEG C, volume space velocity is 26000h-1, material gas quantity be 680Nm3/hr、H2/(3CO+4CO2) mol ratio be 1.05, CO+CO in unstripped gas2Contents on dry basis be 14.5vol%.Under this operating condition, it is 70.8% that the pressure of beds reduces to 652Pa/m, CO conversion ratio, and under this condition, thermodynamical equilibrium is 71.3%.
Embodiment 2:
By particle diameter less than the methanation catalyst powder body 1kg that NiO weight percentage is 45% and the 22g graphite of 0.15mm, 50g label 425 cement mixing after insert in wet type batch mixer, continuous when material powder body rotates is the HNO of 3% by 450ml mass concentration3Aqueous solution is vaporific be injected to mixed powder surface, continuous wet mixed 60 minutes after whole liquid spray into.It is the cylindrical particles catalyst of uniform 7 Φ 4mm through holes on Φ 18mm, height 10mm, cross section that the mixed powder wet feed obtained makes profile outside diameter with tablet machine after granulator granulation.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 1.07mm2/mm3, radially maximum mass transfer distance is 1.73mm, and side pressure strength is 121N/cm.Being labeled as embodiment 2, its cross-sectional structure size is shown in Fig. 2.
The methanation catalyst of above-described embodiment 2 being applied to synthesis gas methanation and produces CO a large amount of methanation stage of SNG process, operating condition is: pressure is 3.0MPa, temperature is 700 DEG C, volume space velocity is 40000h-1, material gas quantity be 680Nm3/hr、H2/(3CO+4CO2) mol ratio be 1.00, CO+CO in unstripped gas2Contents on dry basis be 10.4vol%.Under this operating condition, it is 45.0% that the pressure of beds reduces to 604Pa/m, CO conversion ratio, and under this condition, thermodynamical equilibrium is 45.3%.
Embodiment 3:
By particle diameter less than the methanation catalyst powder body 1kg that NiO weight percentage is 60% and the 22g graphite of 0.15mm, 50g label 425 cement mixing after insert in wet type batch mixer, continuous when material powder body rotates is the HNO of 3% by 400ml mass concentration3Aqueous solution and the polyvinyl alcohol (PVA) that 50ml mass concentration is 3% are injected to mixed powder surface in vaporific, continuous wet mixed 60 minutes after whole liquid spray into.It is that Φ 10mm, height 5mm, cross-section center have 1 Φ 3mm through hole and cross section is the cylindrical particles catalyst of 4 leaf petal shapes that the mixed powder wet feed obtained makes profile circumscribed circle diameter with tablet machine after granulator granulation, and its cross-sectional structure size is shown in Fig. 3.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 1.18mm2/mm3, radially maximum mass transfer distance is 1.75mm, and side pressure strength is 142N/cm.It is labeled as embodiment 3.
The methanation catalyst of above-described embodiment 3 being applied to synthesis gas methanation and produces CO a large amount of methanation stage of SNG process, operating condition is: pressure is 3.0MPa, temperature is 600 DEG C, volume space velocity is 40000h-1, material gas quantity be 680Nm3/hr、H2/(3CO+4CO2) mol ratio be 1.00, CO+CO in unstripped gas2Contents on dry basis be 12.0vol%.Under this operating condition, it is 86.7% that the pressure of beds reduces to 622Pa/m, CO conversion ratio, and under this condition, thermodynamical equilibrium is 86.7%.
Embodiment 4:
By particle diameter less than the methanation catalyst powder body 1kg that NiO weight percentage is 60% and the 22g graphite of 0.15mm, 50g label 425 cement mixing after insert in wet type batch mixer, continuous when material powder body rotates is the HNO of 3% by 400ml mass concentration3Aqueous solution and the polyvinyl alcohol (PVA) that 50ml mass concentration is 3% are injected to mixed powder surface in vaporific, continuous wet mixed 60 minutes after whole liquid spray into.It is the cylindrical particles catalyst of uniform 4 Φ 2mm through holes on Φ 10mm, height 10mm, cross section that the mixed powder wet feed obtained makes profile outside diameter with tablet machine after granulator granulation.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 1.06mm2/mm3, radially maximum mass transfer distance is 1.49mm, and side pressure strength is 165N/cm.Being labeled as embodiment 4, its cross-sectional structure size is shown in Fig. 4.
The methanation catalyst of above-described embodiment 4 being applied to synthesis gas methanation and produces CO a large amount of methanation stage of SNG process, operating condition is: pressure is 3.0MPa, temperature is 600 DEG C, volume space velocity is 30000h-1, material gas quantity be 680Nm3/hr、H2/(3CO+4CO2) mol ratio be 1.00, CO+CO in unstripped gas2Contents on dry basis be 12.0vol%.Under this operating condition, it is 85.4% that the pressure of beds reduces to 624Pa/m, CO conversion ratio, and under this condition, thermodynamical equilibrium is 86.7%.
Embodiment 5:
Inserting in wet type batch mixer less than methanation catalyst powder body 1kg and the 22g graphite that NiO weight percentage is 20% of 0.15mm, 30g sesbania powder after mixing by particle diameter, continuous when material powder body rotates is the HNO of 3% by 600ml mass concentration3Aqueous solution and the polyvinyl alcohol (PVA) that 80ml mass concentration is 3% are injected to mixed powder surface in vaporific, continuous wet mixed 60 minutes after whole liquid spray into.The mixed powder wet feed obtained makes outside diameter to be Φ 10mm, interior circular diameter is the circle ring column beaded catalyst of Φ 5mm, height 10mm through banded extruder extrusion.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 1.00mm2/mm3, radially maximum mass transfer distance is 2.50mm, and side pressure strength is 128N/cm.Being labeled as embodiment 5, its cross-sectional structure size is shown in Fig. 5.
The methanation catalyst of above-described embodiment 5 is applied to synthesis gas methanation and produces the CO of SNG process2Supplementing the methanation stage, operating condition is: pressure is 3.0MPa, temperature is 400 DEG C, volume space velocity is 40000h-1, material gas quantity be 450Nm3/hr、H2/(3CO+4CO2) mol ratio be 1.00, CO+CO in unstripped gas2Contents on dry basis be 6.3vol%.Under this operating condition, CO2Conversion ratio is 68.1%, and CO conversion ratio is 99.0%, all close to the thermodynamical equilibrium under this condition.
Embodiment 6:
Insert in wet type batch mixer after particle diameter methanation catalyst powder body 1kg and the 22g graphite that NiO weight percentage is 25% less than 0.15mm is mixed, is the HNO of 3% by 600ml mass concentration continuously when material powder body rotates3Aqueous solution and the polyvinyl alcohol (PVA) that 80ml mass concentration is 3% are injected to mixed powder surface in vaporific, continuous wet mixed 60 minutes after whole liquid spray into.It is the cylindrical particles catalyst of uniform 3 Φ 2mm through holes on Φ 10mm, height 5mm, cross section that the mixed powder wet feed obtained makes profile outside diameter through banded extruder extrusion.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 1.13mm2/mm3, radially maximum mass transfer distance is 1.87mm, and side pressure strength is 135N/cm.Being labeled as embodiment 6, its cross-sectional structure size is shown in Fig. 6.
The methanation catalyst of above-described embodiment 6 is applied to synthesis gas methanation and produces the CO of SNG process2Supplementing the methanation stage, operating condition is: pressure is 3.0MPa, temperature is 320 DEG C, volume space velocity is 40000h-1, material gas quantity be 450Nm3/hr、H2/(3CO+4CO2) mol ratio be 0.86, CO+CO in unstripped gas2Contents on dry basis be 3.5vol%.Under this operating condition, CO2Conversion ratio is 75.4%, and CO conversion ratio is 96.1%, all close to the thermodynamical equilibrium under this condition.
Comparative example 1:
The abnormally-structured methanation catalyst that this comparative example attempts to illustrate to adopt moulding process of the present invention has relatively low beds resistance drop in a large amount of methanation of CO.
Methanation catalyst powder body, consumption of binder and mixing, molding process are with embodiment 2.The cylinder beaded catalyst that profile outside diameter is Φ 10mm, height 10mm made by the mixed powder wet feed economy-combat sheet machine obtained.This catalyst particle surface is long-pending/and grain skeleton volume ratio is 0.60mm2/mm3, radially maximum mass transfer distance is 5.00mm, and side pressure strength is 133N/cm.It is labeled as comparative example 1.
The methanation catalyst of above-mentioned comparative example 1 being applied to synthesis gas methanation and produces CO a large amount of methanation stage of SNG process, operating condition is also with embodiment 2.Under this operating condition, the pressure of beds reduces to 1613Pa/m.
Comparative example 2:
The abnormally-structured methanation catalyst that this comparative example attempts to illustrate to adopt moulding process of the present invention is at CO2Supplement in methanation and there is higher response speed.
Taking Ni-based methanation catalyst that commercially available NiO weight percentage is 20% as a comparison case 2, this catalyst is Φ 3mm spherical particle.Weigh 2.04g comparative example 2 catalyst, be loaded in gradientless reactor and measure its macrodynamics response speed at 250 DEG C, 300 DEG C and 350 DEG C respectively.Other operating conditions are: pressure 3.0MPa, gas recycle ratio 25, reaction gas consist of 9.59vol%H2, 2.82vol%CO2, 0.09vol%CO, 86.21vol%CH4And 1.3vol%H2O.Its CO at 250 DEG C, 300 DEG C and 350 DEG C under this operating condition2Conversion ratio respectively 32.9%, 45.3% and 50.1%.
Take the embodiment of the present invention 6 catalyst of identical weight, under the same operating conditions, its CO at 250 DEG C, 300 DEG C and 350 DEG C2Conversion ratio respectively 35.2%, 53.6% and 60.3%.
Claims (11)
1. a special-shaped methanation catalyst, it is characterized in that the porous cylinder beaded catalyst that this catalyst is the regular symmetry of geometry that Ni-based synthesis gas methanation catalyst powder body is made by the mode of tabletting or extrusion, this porous cylinder beaded catalyst profile circumscribed circle diameter is Φ 3-22mm, height 3-12mm, and surface area/grain skeleton volume ratio is 0.8-1.6mm2/mm3, radially maximum mass transfer distance is 1.4-4.0mm, and side pressure strength is 80-200N/cm.
2. a kind of special-shaped methanation catalyst according to claims 1, it is characterized in that described Ni-based methanation catalyst powder body adopts the synthesis technique of chemical coprecipitation, precipitation from homogeneous solution or high-temperature water thermal synthesis to prepare, in described Ni-based methanation catalyst, the weight percentage of NiO is 40-60%.
3. a kind of special-shaped methanation catalyst according to claims 2, it is characterised in that the described preferred profile circumscribed circle diameter of porous cylinder beaded catalyst be Φ 8-22mm, height 5-10mm, this porous cylinder beaded catalyst preferred surface long-pending/grain skeleton volume ratio is 0.8-1.3mm2/mm3, radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is 120-200N/cm.
4. a kind of special-shaped methanation catalyst according to claims 1, it is characterised in that described Ni-based methanation catalyst powder body adopts the technique such as infusion process, beating method to prepare, and in Ni-based methanation catalyst, the weight percentage of NiO is 20-30%.
5. a kind of special-shaped methanation catalyst according to claims 4, it is characterised in that described porous cylinder beaded catalyst is preferably Φ 3-14mm, highly 5-10mm, the surface area/grain skeleton volume ratio of this porous cylinder beaded catalyst is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is 80-140N/cm.
6. the moulding process of a kind of special-shaped methanation catalyst according to claim 1, it is characterised in that carry out according to following steps:
Insert in wet type batch mixer after the particle diameter Ni-based synthesis gas methanation catalyst powder body less than 0.15mm is mixed with graphite, is the HNO of 3% by mass concentration continuously when material powder body rotates3Aqueous solution is vaporific be injected to mixed powder surface, continuous wet mixed 60 minutes after whole liquid spray into；
Above-mentioned Ni-based synthesis gas methanation catalyst powder body is made by the mode of tabletting or extrusion the porous cylinder beaded catalyst of the regular symmetry of geometry, this porous cylinder beaded catalyst profile circumscribed circle diameter is Φ 3-22mm, height 3-12mm, and the surface area of this porous cylinder beaded catalyst/grain skeleton volume ratio is 0.8-1.6mm2/mm3, radially maximum mass transfer distance is 1.4-4.0mm, and side pressure strength is 80-200N/cm；
Described catalyst, graphite and HNO3Weight ratio be 100:2-3:40-60.
7. the moulding process of a kind of special-shaped methanation catalyst according to claim 6, it is characterized in that the porous cylinder beaded catalyst of the regular symmetry of geometry is made in described Ni-based methanation catalyst powder body molding by tabletting mode, porous cylinder beaded catalyst configuration adopts the cylinder axis exterior surface such as porous gear column, porous petal column to have the form of ditch or groove.The preferred profile circumscribed circle diameter of porous cylinder beaded catalyst be Φ 8-22mm, height 5-10mm, this porous cylinder beaded catalyst preferred surface long-pending/grain skeleton volume ratio is 0.8-1.3mm2/mm3, radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is 120-200N/cm.
8. the moulding process of a kind of special-shaped methanation catalyst according to claim 6, it is characterised in that described Ni-based methanation catalyst powder body molding adopts the mode of extrusion to make the porous cylinder beaded catalyst of the regular symmetry of geometry.Porous cylinder beaded catalyst is preferably Φ 3-14mm, highly 5-10mm, the surface area/grain skeleton volume ratio of this porous cylinder beaded catalyst is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is 80-140N/cm.
9. the application of a kind of special-shaped methanation catalyst according to claim 1, it is characterized in that the porous cylinder beaded catalyst of the regular symmetry of above-mentioned geometry is applied to synthesis gas methanation and produces each operation stage of SNG process, the application conditions of this porous cylinder beaded catalyst is: pressure is 1.0-5.0MPa, temperature is 250-700 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be 0.80-1.05.
10. the application of a kind of special-shaped methanation catalyst according to claim 9, it is characterised in that
Profile circumscribed circle diameter is Φ 8-22mm, highly 5-10mm, surface area/grain skeleton volume ratio is 0.8-1.3mm2/mm3Radially maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is that the application conditions of the porous cylinder beaded catalyst of the regular symmetry of geometry of 120-200N/cm is preferred for synthesis gas methanation and produces CO a large amount of methanation stage of SNG process: pressure is 1.0-5.0MPa, temperature is 280-700 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be the CO+CO in 1.00-1.05, raw material of synthetic gas gas2Contents on dry basis be 8-25vol%.
11. the application of a kind of special-shaped methanation catalyst according to claim 9, it is characterised in that profile circumscribed circle diameter is Φ 3-14mm, highly 5-10mm, surface area/grain skeleton volume ratio is 1.0-1.6mm2/mm3, radially maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is that the application conditions of the porous cylinder beaded catalyst of the regular symmetry of geometry of 80-140N/cm is preferred for synthesis gas methanation and produces the CO of SNG process2Supplement the methanation stage: pressure is 1.0-5.0MPa, temperature is 250-450 DEG C, volume space velocity is 20000-60000h-1、H2/(3CO+4CO2) mol ratio be the CO+CO in 0.80-1.00, raw material of synthetic gas gas2Contents on dry basis be 3-8vol%.
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| CN115672331A (en) * | 2021-07-23 | 2023-02-03 | 国家能源投资集团有限责任公司 | Methanation catalyst and preparation method and application thereof |
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| CN101391218A (en) * | 2008-10-31 | 2009-03-25 | 西南化工研究设计院 | Coke-oven gas methanation catalyst and preparation method thereof |
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