CN105709794B - A kind of abnormal shape methanation catalyst and its moulding process and application - Google Patents
A kind of abnormal shape methanation catalyst and its moulding process and application Download PDFInfo
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- CN105709794B CN105709794B CN201410719909.2A CN201410719909A CN105709794B CN 105709794 B CN105709794 B CN 105709794B CN 201410719909 A CN201410719909 A CN 201410719909A CN 105709794 B CN105709794 B CN 105709794B
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Abstract
The invention discloses a kind of special-shaped methanation catalyst and its moulding process and applications.The technique is that Ni-based synthesis gas methanation catalyst powder is made to profile circumscribed circle diameter is 3 22mm of Φ, height 3 12mm, surface area/grain skeleton volume ratio are 0.8 1.6mm by way of tabletting or extrusion2/mm3, radial maximum mass transfer distance be 1.4 4.0mm, the regular symmetrical porous cylindrical particles of geometry.Process characteristic and requirement of the abnormal shape methanation catalyst moulding process provided by the invention for synthesis gas methanation each stage, the utilization ratio of catalyst activity component can not only be improved, and is all played an important role to reducing bed resistance drop, improving long-lasting catalytic operation stability.
Description
Technical field
The present invention relates to a kind of synthesis gas methanation catalyst, more particularly to a kind of special-shaped methanation catalyst and its at
Type technique and application.
Background technology
In recent years, due to the rising of China's natural gas consumption figure and the increase of supply demand gap, cause Gas Prices continuous
Go up, by coal through synthesis gas (CO+H2) methanation produces substitute natural gas (Substitute Natural Gas, SNG)
Process paid attention to extensively by industry again, it is considered to be alleviate one of the important means of China's natural gas disparities between supply and demand.Synthesis gas
It is as follows that the key reaction that SNG technical process occurs is produced by methanation reaction：
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, referred to as a large amount of methanation (Bulk
Methanation), belong to strong exothermal reaction.Due in reaction gas CO contents it is higher (such as Lurgi gasifier production synthesis gas
In be usually 20vol% or so), and often the CO of conversion 1vol% can generate 72 DEG C of adiabatic temperature rise, therefore a large amount of methanations
The mode of generally use multistage and gas circulation controls reaction bed temperature, therefore gas circulating compressor becomes coal to SNG mistake
The essential crucial dynamic equipment of journey, power consumption also become the important technology index for weighing coal to SNG technical process quality.Cycle
Compressor power consumption and methanator catalyst bed resistance drop are closely related, traditional spherical shape or cylindrical catalyst grain bed
Layer is tight type accumulation filling, and the resistance drop of catalyst bed is larger；And using has abnormally-structured catalyst such as porous column
The bed of the fillings such as shape, porous gear-like, porous honeycomb, porous spherical, bed voidage can be improved 20% or more, bed
Resistance drop can be reduced effectively, to reduce the regular job power consumption of recycle compressor in a large amount of methanations.In addition, a large amount of
Methanation reaction temperature usually at 600 DEG C or more, transport for a long time under excessively high reaction temperature by the surface temperature of catalyst then higher
It is about to catalyst activity component particle buildup is made to grow up, carrier sintering.Therefore, except from catalyst component formulation set about improve urge
Except the high-temperature stability of agent, it also can promptly be transmitted using abnormally-structured catalyst granules and release catalytic inner
The reaction heat that duct and catalyst surface generate, to keep the high temperature active and stability of catalyst.According to disclosed data
Report, possesses a large amount of methanation technologies of Davy companies of Britain of coal to SNG methanation patented technology using four hole plums at present
Flower-shaped catalyst, and Topsoe companies of Denmark are then using seven apertures in the human head cylindrical catalyst.Domestic each colleges and universities, Research Center in one's power can
Source group also develops numerous high temperature full methanation catalyst, as CN200910187675.0, CN201010223996.4,
CN201010127840.6, CN201110351012.5, CN201110336259.X etc., but mainly concentrate on being formulated and closing
At the invention of method, substantially without reference to the information in terms of catalyst configuration.
Abnormally-structured methanation catalyst equally can also give CO2Methanation reaction reacts (3) and brings benefit, this is anti-
Supplement methanation (Trim Methanation) should be referred to as, effect is on the basis of CO a large amount of methanations, by reaction system
In CO2It is further hydrogenated to CH with a small amount of CO4, to meet the quality requirement of SNG products.It is followed in the multistage of synthesis gas SNG
In ring technique, since the methanation load of this segment process is little, the reaction is mainly in, (250-450 DEG C) hair of low-temperature space
It is raw.Mainly emphasize that high-temperature stability is different from a large amount of methanation catalysts of CO, CO2Supplement methanation catalyst mainly emphatically
It is the high activity under low temperature so that CO2Hydro-conversion as much as possible.CO currently used for synthesis gas SNG2Methanation is urged
Agent patent, such as patent CN201010034230.1, CN200910117686.1, still focus principally on from catalyst formulation and
Its invention is realized in synthetic method.In fact, for kinetics angle, CO2Methanation be it is interior diffusion in order to control
Therefore the reaction process of step for catalysagen particle, provides more granule surface area/volume ratios and smaller axis
To, radial mass transfer distance, can equally play the role of improving unit grain catalyst volume catalytic active component utilization rate.
In conclusion for the synthesis gas methanation in coal to SNG technique, for a large amount of methanations of CO and CO2It mends
Methanation feature is filled, a kind of special-shaped methanation catalyst moulding process of development is of great significance.
Invention content
The object of the present invention is to provide a kind of special-shaped methanation catalyst moulding process in synthesis gas methanation reaction
Using.Compared with traditional spherical shape or cylindrical catalyst particle, existed using special-shaped methanation catalyst particle provided by the invention
During synthesis gas methanation SNG, a large amount of methanations of CO and CO can be directed to2Process characteristic and the requirement of methanation are supplemented,
The effect of playing catalyst to the maximum extent, can not only improve the utilization ratio of active component in catalyst granules, and right
Reduce catalyst bed resistance drop, raising long-lasting catalytic operation stability has very important important function.To realize
Above-mentioned purpose, the technical solution adopted by the present invention are as follows：
A kind of abnormal shape methanation catalyst, the catalyst are Ni-based synthesis gas methanation catalyst powder by tabletting or squeeze
The regular symmetrical porous cylinder beaded catalyst of geometry made of the mode of item, outside the porous cylinder beaded catalyst profile
It is Φ 3-22mm, height 3-12mm to connect circular diameter, and surface area/grain skeleton volume ratio is 0.8-1.6mm2/mm3, radial maximum biography
Matter distance is 1.4-4.0mm, side pressure strength 80-200N/cm.
The Ni-based methanation catalyst powder uses the synthesis work of chemical coprecipitation, precipitation from homogeneous solution or high temperature hydrothermal synthesis
Prepared by skill, the weight percentage of NiO is 40-60% in the Ni-based methanation catalyst.The porous cylinder particulate catalytic
The preferred profile circumscribed circle diameter of agent is Φ 8-22mm, height 5-10mm, the porous preferred surface area/particle of cylinder beaded catalyst
Skeleton volume ratio is 0.8-1.3mm2/mm3, radial maximum mass transfer distance is 1.4-3.0mm, side pressure strength 120-200N/cm.
The Ni-based methanation catalyst powder is prepared using techniques such as infusion process, beating methods, Ni-based methanation catalyst
The weight percentage of middle NiO is 20-30%.The porous cylinder beaded catalyst be preferably Φ 3-14mm, height 5-10mm,
The surface area of the porous cylinder beaded catalyst/grain skeleton volume ratio is 1.0-1.6mm2/mm3, radial maximum mass transfer distance is
1.8-4.0mm, side pressure strength 80-140N/cm.
A kind of moulding process of abnormal shape methanation catalyst, follows the steps below：
Ni-based synthesis gas methanation catalyst powder by grain size less than 0.15mm is placed in wet type batch mixing after being mixed with graphite
In machine, the HNO for being continuously 3% by mass concentration in the case where material powder rotates3Aqueous solution is injected to mixed powder in mist
Body surface face, continuous wet mixed 60 minutes after the penetrating of whole liquid；
It is regular that geometry is made by way of tabletting or extrusion in above-mentioned Ni-based synthesis gas methanation catalyst powder
Symmetrical porous cylinder beaded catalyst, the porous cylinder beaded catalyst profile circumscribed circle diameter are Φ 3-22mm, height 3-
Surface area/grain skeleton volume ratio of 12mm, the porous cylinder beaded catalyst are 0.8-1.6mm2/mm3, radial maximum mass transfer
Distance is 1.4-4.0mm, side pressure strength 80-200N/cm；
The catalyst, graphite and HNO3Weight ratio be 100：2-3：40-60.
The regular symmetrical porous column of geometry is made by tabletting mode in the Ni-based methanation catalyst powder molding
Body beaded catalyst, porous cylinder beaded catalyst configuration are outside using cylinder axis such as porous gear column, porous petal columns
Surface is provided with the form of ditch or slot.The porous preferred profile circumscribed circle diameter of cylinder beaded catalyst is Φ 8-22mm, height 5-
10mm, the porous preferred surface area of the cylinder beaded catalyst/grain skeleton volume ratio are 0.8-1.3mm2/mm3, radial maximum biography
Matter distance is 1.4-3.0mm, side pressure strength 120-200N/cm
It is regular symmetrical porous that geometry is made in the Ni-based methanation catalyst powder molding by the way of extrusion
Cylindrical particles catalyst.Porous cylinder beaded catalyst is preferably Φ 3-14mm, height 5-10mm, the porous cylinder particulate catalytic
The surface area of agent/grain skeleton volume ratio is 1.0-1.6mm2/mm3, radial maximum mass transfer distance is 1.8-4.0mm, side pressure strength
For 80-140N/cm.
A kind of application of abnormal shape methanation catalyst, the regular symmetrical porous cylinder beaded catalyst of above-mentioned geometry are answered
Each operation stage of SNG processes is produced for synthesis gas methanation, the application conditions of the porous cylinder beaded catalyst are：Pressure
Power is 1.0-5.0MPa, temperature is 250-700 DEG C, volume space velocity 20000-60000h-1、H2/(3CO+4CO2) molar ratio
For 0.80-1.05.
Profile circumscribed circle diameter is Φ 8-22mm, height 5-10mm, surface area/grain skeleton volume ratio are 0.8-
1.3mm2/mm3, radial maximum mass transfer distance is 1.4-3.0mm, and side pressure strength is that the geometry of 120-200N/cm is regular symmetrical
Porous cylinder beaded catalyst application conditions be preferred for synthesis gas methanation production SNG processes a large amount of methanations of CO
Stage：Pressure is 1.0-5.0MPa, temperature is 280-700 DEG C, volume space velocity 20000-60000h-1、H2/(3CO+4CO2)
Molar ratio is 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, height 5-10mm, surface area/grain skeleton volume ratio are 1.0-
1.6mm2/mm3, radial maximum mass transfer distance is 1.8-4.0mm, and side pressure strength is that the geometry of 80-140N/cm is regular symmetrical
Porous cylinder beaded catalyst application conditions be preferred for synthesis gas methanation production SNG processes CO2Supplement methanation
Stage：Pressure is 1.0-5.0MPa, temperature is 250-450 DEG C, volume space velocity 20000-60000h-1、H2/(3CO+4CO2)
Molar ratio is the CO+CO in 0.80-1.00, raw material of synthetic gas gas2Contents on dry basis be 3-8vol%.
In certain preferable embodiments of the present invention, to ensure that the pyroreaction stage in a large amount of methanations of CO has
Sufficiently high activity and hydrothermal stability, Ni-based methanation catalyst powder use chemical coprecipitation, precipitation from homogeneous solution or high-temperature water
It is prepared by the synthesis technology of thermal synthesis, and in Ni-based methanation catalyst NiO weight percentage preferably between 40-60%.
In the preferable embodiment of other of the present invention, to ensure that catalyst has in CO a large amount of methanation stages
Lower bed resistance drop and higher high-temperature-resistant gas scouring capability, Ni-based methanation catalyst powder molding preferably use tabletting
Mode, porous cylinder beaded catalyst configuration preferably uses the cylinders axial external surfaces such as porous gear column, porous petal column
It is provided with the form of ditch or slot.
In certain preferable embodiments of the present invention, to ensure in CO2Supplementing the methanation reaction stage has preferably
Low temperature active, Ni-based methanation catalyst powder prepared using the techniques such as infusion process, beating method.Based on same reason,
In the preferable embodiment of other of the present invention, Ni-based methanation catalyst powder molding is preferably by the way of extrusion.This
Outside, due to the CO in the supplement methanation stage, process gas2The methanation load of (including a small amount of CO) is little, from Technological Economy
From the point of view of, in the preferable embodiment of other of the present invention, the weight percent of NiO in Ni-based methanation catalyst
Content is preferably between 20-30%.
The present invention has the following advantages：
Abnormally-structured methanation catalyst has higher granule surface area/skeleton volume ratio and smaller radial mass transfer
Distance, in synthesis gas full methanation production SNG techniques, a large amount of methanations of CO and CO can be directed to2Supplement methanation
Process characteristic and requirement, to the maximum extent the effect of performance methanation catalyst：
(1) in a large amount of methanation process of CO, catalyst bed resistance drop can effectively be reduced to reduce gas circulation
Compressor power consumption, when can remove methanation reaction heat rapidly to improve long under high temperature thermal and hydric environment of methanation catalyst
Between operation stability；
(2) in CO2It supplements in methanation process, effective catalyst activity surface can be increased, reduce inside diffusional resistance,
The utilization ratio of active component in catalyst granules is improved, and then improves the activity of catalyst；
(3) a large amount of methanations of CO and CO are directed to2Process characteristic and the requirement for supplementing methanation, using different sizes, difference
The methanation catalyst of configuration and NiO contents meets the Technological Economy requirement of coal to SNG methanation process process, can be further
Save catalyst cost and regular job expense.
Description of the drawings
Fig. 1 is 1 cross sectional dimensions schematic diagram of embodiment,
Fig. 2 is 2 cross sectional dimensions schematic diagram of embodiment,
Fig. 3 is 3 cross sectional dimensions schematic diagram of embodiment,
Fig. 4 is 4 cross sectional dimensions schematic diagram of embodiment,
Fig. 5 is 5 cross sectional dimensions schematic diagram of embodiment,
Fig. 6 is 6 cross sectional dimensions schematic diagram of embodiment.
Specific implementation mode
Illustrate embodiments of the present invention, person of ordinary skill in the field below by way of particular specific embodiment
It can be by other features and advantages of the content understanding disclosed in the present specification present invention.The present invention can also pass through other different tools
Body embodiment is implemented or is applied, and details in this specification can also be based on different perspectives and applications, is not departing from this
It carry out various modifications and changes under the spirit of invention.
Unless otherwise noted, all numbers occurred in description of the invention and claims, for example, component weight
The physical parameter value of amount percentage, particle scale and certain description particle configurations all should be understood that " about " value.At this
The exact numerical occurred in description of the invention and claims should be understood that the section Example for constituting the present invention.Although
The accuracy for ensureing numerical value is tried hard to be in the example that the present invention provides, but due to the standard deviation of various measuring techniques, is appointed
How to measure obtained numerical value and is all 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 surface area (including the appearance of all exposures of abnormally-structured particle
The ratio between the surface area of area and endoporus) and grain skeleton volume.
Term " radial maximum mass transfer distance " means and can be obtained most on the symmetrical column type particle cross section of geometry
The radius of big inscribed circle.
Unless otherwise noted, the formula and preparation method of Ni-based methanation catalyst powder involved in the present invention, such as
Chemical coprecipitation, precipitation from homogeneous solution, high temperature hydrothermal synthesis, infusion process and beating method etc. are that researcher in this field institute is ripe
Know.Those skilled in the art can obtain the methanation of various NiO contents involved in the present invention by the experiment of limited number of time
Catalyst powder, thus the formula of above-mentioned Ni-based methanation catalyst powder and synthesis technology not the scope of protection of the invention it
It is interior.
Embodiment 1：
The methanation catalyst powder 1kg and 22g stones that NiO weight percentages by grain size less than 0.15mm are 55%
After ink mixing in merging wet type batch mixer, the HNO for being continuously 3% by 400ml mass concentrations in the case where material powder rotates3
Aqueous solution is injected to mixed powder surface in mist, continuous wet mixed 60 minutes after the penetrating of whole liquid.Obtained mixing
Powder wet feed after comminutor is granulated with tablet machine be made profile outside diameter be Φ 18mm, height 10mm, uniformly distributed 5 on cross section
The cylindrical particles catalyst of a Φ 4mm through-holes.Catalyst particle surface product/grain skeleton the volume ratio is 0.82mm2/mm3, diameter
It is 2.62mm, side pressure strength 154N/cm to maximum mass transfer distance.Labeled as embodiment 1, cross-sectional structure size is shown in Fig. 1.
The methanation catalyst of above-described embodiment 1 is applied to CO a large amount of methanation stages that synthesis gas methanation produces SNG processes, behaviour
It is as condition：Pressure is 3.0MPa, temperature is 650 DEG C, volume space velocity 26000h-1, material gas quantity 680Nm3/hr、H2/
(3CO+4CO2) molar ratio be 1.05, the CO+CO in unstripped gas2Contents on dry basis be 14.5vol%.Under this operating condition,
The pressure of catalyst bed is reduced to 652Pa/m, and CO conversion ratios are 70.8%, and thermodynamical equilibrium is 71.3% under the conditions of this.
Embodiment 2：
The methanation catalyst powder 1kg and 22g stones that NiO weight percentages by grain size less than 0.15mm are 45%
After black, 50g labels 425 cement mixing in merging wet type batch mixer, in the case where material powder rotates continuously by 450ml matter
Measure a concentration of 3% HNO3Aqueous solution is injected to mixed powder surface in mist, the continuous wet mixed after the penetrating of whole liquid
60 minutes.Obtained mixed powder wet feed after comminutor is granulated with tablet machine be made profile outside diameter be Φ 18mm, height
The cylindrical particles catalyst of uniformly distributed 7 Φ 4mm through-holes on 10mm, cross section.Catalyst particle surface product/grain skeleton the volume
Than for 1.07mm2/mm3, radial maximum mass transfer distance is 1.73mm, side pressure strength 121N/cm.It is horizontal labeled as embodiment 2
Cross section structure size is shown in Fig. 2.
The methanation catalyst of above-described embodiment 2 is applied to a large amount of methane of CO that synthesis gas methanation produces SNG processes
Change stage, operating condition are：Pressure is 3.0MPa, temperature is 700 DEG C, volume space velocity 40000h-1, material gas quantity be
680Nm3/hr、H2/(3CO+4CO2) molar ratio be 1.00, the CO+CO in unstripped gas2Contents on dry basis be 10.4vol%.
Under this operating condition, the pressure of catalyst bed is reduced to 604Pa/m, and CO conversion ratios are 45.0%, and thermodynamics is flat under the conditions of this
Weighing apparatus is 45.3%.
Embodiment 3：
The methanation catalyst powder 1kg and 22g stones that NiO weight percentages by grain size less than 0.15mm are 60%
After black, 50g labels 425 cement mixing in merging wet type batch mixer, in the case where material powder rotates continuously by 400ml matter
Measure a concentration of 3% HNO3The polyvinyl alcohol (PVA) that aqueous solution and 50ml mass concentrations are 3% is injected to mixed powder in mist
Surface, continuous wet mixed 60 minutes after the penetrating of whole liquid.Obtained mixed powder wet feed is used after comminutor is granulated and is beaten
It is in 4 that piece machine, which is made profile circumscribed circle diameter and is provided with 1 Φ 3mm through-hole and cross section for Φ 10mm, height 5mm, cross-section center,
The cylindrical particles catalyst of leaf petal shape, cross-sectional structure size are shown in Fig. 3.Catalyst particle surface product/the grain skeleton
Volume ratio is 1.18mm2/mm3, radial maximum mass transfer distance is 1.75mm, side pressure strength 142N/cm.Labeled as embodiment 3.
The methanation catalyst of above-described embodiment 3 is applied to a large amount of methane of CO that synthesis gas methanation produces SNG processes
Change stage, operating condition are：Pressure is 3.0MPa, temperature is 600 DEG C, volume space velocity 40000h-1, material gas quantity be
680Nm3/hr、H2/(3CO+4CO2) molar ratio be 1.00, the CO+CO in unstripped gas2Contents on dry basis be 12.0vol%.
Under the operating condition, the pressure of catalyst bed is reduced to 622Pa/m, and CO conversion ratios are 86.7%, thermodynamical equilibrium under the conditions of this
It is 86.7%.
Embodiment 4：
The methanation catalyst powder 1kg and 22g stones that NiO weight percentages by grain size less than 0.15mm are 60%
After black, 50g labels 425 cement mixing in merging wet type batch mixer, in the case where material powder rotates continuously by 400ml matter
Measure a concentration of 3% HNO3The polyvinyl alcohol (PVA) that aqueous solution and 50ml mass concentrations are 3% is injected to mixed powder in mist
Surface, continuous wet mixed 60 minutes after the penetrating of whole liquid.Obtained mixed powder wet feed is used after comminutor is granulated and is beaten
Cylindrical particles catalysis of the profile outside diameter for uniformly distributed 4 Φ 2mm through-holes on Φ 10mm, height 10mm, cross section is made in piece machine
Agent.Catalyst particle surface product/grain skeleton the volume ratio is 1.06mm2/mm3, radial maximum mass transfer distance is 1.49mm, side
Compressive Strength is 165N/cm.Labeled as embodiment 4, cross-sectional structure size is shown in Fig. 4.
The methanation catalyst of above-described embodiment 4 is applied to a large amount of methane of CO that synthesis gas methanation produces SNG processes
Change stage, operating condition are：Pressure is 3.0MPa, temperature is 600 DEG C, volume space velocity 30000h-1, material gas quantity be
680Nm3/hr、H2/(3CO+4CO2) molar ratio be 1.00, the CO+CO in unstripped gas2Contents on dry basis be 12.0vol%.
Under the operating condition, the pressure of catalyst bed is reduced to 624Pa/m, and CO conversion ratios are 85.4%, thermodynamical equilibrium under the conditions of this
It is 86.7%.
Embodiment 5：
The methanation catalyst powder 1kg and 22g stones that NiO weight percentages by grain size less than 0.15mm are 20%
After ink, the mixing of 30g sesbania powders in merging wet type batch mixer, in the case where material powder rotates continuously by 600ml mass concentrations
For 3% HNO3The polyvinyl alcohol (PVA) that aqueous solution and 80ml mass concentrations are 3% is injected to mixed powder surface in mist,
Continuous wet mixed 60 minutes after the penetrating of whole liquid.Outside diameter is made through banded extruder extrusion in obtained mixed powder wet feed
For the circle ring column beaded catalyst of Φ 10mm, a diameter of Φ 5mm of inner circle, height 10mm.Catalyst particle surface product/the particle
Skeleton volume ratio is 1.00mm2/mm3, radial maximum mass transfer distance is 2.50mm, side pressure strength 128N/cm.Labeled as implementation
Example 5, cross-sectional structure size are shown in Fig. 5.
The methanation catalyst of above-described embodiment 5 is applied to the CO that synthesis gas methanation produces SNG processes2Supplement methane
Change stage, operating condition are：Pressure is 3.0MPa, temperature is 400 DEG C, volume space velocity 40000h-1, material gas quantity be
450Nm3/hr、H2/(3CO+4CO2) molar ratio be 1.00, the CO+CO in unstripped gas2Contents on dry basis be 6.3vol%.
Under the operating condition, CO2Conversion ratio is that 68.1%, CO conversion ratios are 99.0%, close to thermodynamical equilibrium under this condition.
Embodiment 6：
The methanation catalyst powder 1kg and 22g graphite that NiO weight percentages by grain size less than 0.15mm are 25%
It is placed in wet type batch mixer after mixing, the HNO for being continuously 3% by 600ml mass concentrations in the case where material powder rotates3Water
The polyvinyl alcohol (PVA) that solution and 80ml mass concentrations are 3% is injected to mixed powder surface in mist, waits for that whole liquid spray into
Continuous wet mixed 60 minutes afterwards.Obtained mixed powder wet feed through banded extruder extrusion be made profile outside diameter be Φ 10mm,
The cylindrical particles catalyst of uniformly distributed 3 Φ 2mm through-holes on height 5mm, cross section.Catalyst particle surface product/the grain skeleton
Volume ratio is 1.13mm2/mm3, radial maximum mass transfer distance is 1.87mm, side pressure strength 135N/cm.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 the CO that synthesis gas methanation produces SNG processes2Supplement methane
Change stage, operating condition are：Pressure is 3.0MPa, temperature is 320 DEG C, volume space velocity 40000h-1, material gas quantity be
450Nm3/hr、H2/(3CO+4CO2) molar ratio be 0.86, the CO+CO in unstripped gas2Contents on dry basis be 3.5vol%.
Under the operating condition, CO2Conversion ratio is that 75.4%, CO conversion ratios are 96.1%, close to thermodynamical equilibrium under this condition.
Comparative example 1：
This comparative example attempts to illustrate the abnormally-structured methanation catalyst using moulding process of the present invention in a large amount of methane of CO
There is lower catalyst bed resistance drop during changing.
Methanation catalyst powder, consumption of binder and mixing, molding process are the same as embodiment 2.Obtained mixed powder
The cylinder beaded catalyst that profile outside diameter is Φ 10mm, height 10mm is made through tablet machine for body wet feed.The catalyst particles
Grain surface area/grain skeleton volume ratio is 0.60mm2/mm3, radial maximum mass transfer distance is 5.00mm, side pressure strength 133N/
cm.Labeled as comparative example 1.
The methanation catalyst of above-mentioned comparative example 1 is applied to a large amount of methane of CO that synthesis gas methanation produces SNG processes
In the change stage, operating condition is also the same as embodiment 2.Under this operating condition, the pressure of catalyst bed is reduced to 1613Pa/m.
Comparative example 2：
This comparative example attempts to illustrate the abnormally-structured methanation catalyst using moulding process of the present invention in CO2Supplement methane
There is higher reaction speed during changing.
The Ni-based methanation catalyst as a comparison case 2 that commercially available NiO weight percentages are 20%, the catalyst is taken to be
Φ 3mm spherical particles.Weigh 2 catalyst of 2.04g comparative examples, loaded on measured respectively in gradientless reactor its 250 DEG C, 300
DEG C and 350 DEG C at macrodynamics reaction speed.Other operating conditions are：Pressure 3.0MPa, gas circulation are than 25, reaction gas
Group becomes 9.59vol%H2, 2.82vol%CO2, 0.09vol%CO, 86.21vol%CH4And 1.3vol%H2O.In the operation
Under the conditions of its CO at 250 DEG C, 300 DEG C and 350 DEG C2Conversion ratio is respectively 32.9%, 45.3% and 50.1%.
Take 6 catalyst of the embodiment of the present invention of identical weight, under the same operating conditions, at 250 DEG C, 300 DEG C and
CO at 350 DEG C2Conversion ratio is respectively 35.2%, 53.6% and 60.3%.
Claims (9)
1. a kind of abnormal shape methanation catalyst, it is characterised in that the catalyst is used for the pyroreaction stage of a large amount of methanations of CO,
The regular symmetrical porous gear of geometry is made in specially Ni-based synthesis gas methanation catalyst powder by way of tabletting
Column or the columnar porous cylinder beaded catalyst of porous petal, the cylinder axial external surface are provided with the form of ditch or slot, should
Porous cylinder beaded catalyst profile circumscribed circle diameter is Φ 3-22mm, height 3-12mm, and surface area/grain skeleton volume ratio is
0.8-1.6 mm2/mm3, radial maximum mass transfer distance is 1.4-4.0 mm, and side pressure strength is 80-200 N/cm；
The Ni-based methanation catalyst powder uses the synthesis technology system of chemical coprecipitation, precipitation from homogeneous solution or high temperature hydrothermal synthesis
Standby, the weight percentage of NiO is 40-60 % in the Ni-based methanation catalyst.
2. a kind of special-shaped methanation catalyst according to claim 1, it is characterised in that the porous cylinder particulate catalytic
The profile circumscribed circle diameter of agent is surface area/grain skeleton of Φ 8-22mm, height 5-10mm, the porous cylinder beaded catalyst
Volume ratio is 0.8-1.3 mm2/mm3, radial maximum mass transfer distance is 1.4-3.0 mm, and side pressure strength is 120-200 N/cm.
3. a kind of abnormal shape methanation catalyst, it is characterised in that the catalyst is used for CO2The cold stage of methanation is supplemented, specifically
The regular symmetrical porous cylindrical particles of geometry are made by way of extrusion for Ni-based synthesis gas methanation catalyst powder
Catalyst, the porous cylinder beaded catalyst profile circumscribed circle diameter are Φ 3-22mm, height 3-12mm, surface area/particulate cancellous bone
Frame volume ratio is 0.8-1.6 mm2/mm3, radial maximum mass transfer distance is 1.4-4.0 mm, and side pressure strength is 80-200 N/cm；
The Ni-based methanation catalyst powder is prepared using infusion process or beating method technique, NiO in Ni-based methanation catalyst
Weight percentage be 20-30 %.
4. a kind of special-shaped methanation catalyst according to claim 3, it is characterised in that the porous cylinder particulate catalytic
The profile circumscribed circle diameter of agent is surface area/grain skeleton of Φ 3-14mm, height 5-10mm, the porous cylinder beaded catalyst
Volume ratio is 1.0-1.6 mm2/mm3, radial maximum mass transfer distance is 1.8-4.0 mm, and side pressure strength is 80-140 N/cm.
5. a kind of moulding process of special-shaped methanation catalyst according to claim 1 or 3, it is characterised in that according to following
Step carries out：
After Ni-based synthesis gas methanation catalyst powder by grain size less than 0.15mm is mixed with graphite in merging wet type batch mixer,
In the case where material powder rotates continuously by mass concentration be 3 % HNO3Aqueous solution is injected to mixed powder body surface in mist
Face, continuous wet mixed 60 minutes after the penetrating of whole liquid；
It is regular symmetrical that geometry is made in above-mentioned Ni-based synthesis gas methanation catalyst powder by way of tabletting or extrusion
Porous cylinder beaded catalyst, the porous cylinder beaded catalyst profile circumscribed circle diameter be Φ 3-22mm, height 3-12mm,
The surface area of the porous cylinder beaded catalyst/grain skeleton volume ratio is 0.8-1.6 mm2/mm3, radial maximum mass transfer distance
For 1.4-4.0 mm, side pressure strength is 80-200 N/cm；
The catalyst powder, graphite and HNO3Weight ratio be 100：2-3：40-60.
6. a kind of moulding process of special-shaped methanation catalyst according to claim 5, it is characterised in that the Ni-based first
The regular symmetrical porous cylinder beaded catalyst of geometry, porous column is made by tabletting mode in the molding of Alkanizing catalyst powder
Body beaded catalyst configuration is provided with the shape of ditch or slot using porous gear column or porous petal column and cylinder axial external surface
Formula；The profile circumscribed circle diameter of porous cylinder beaded catalyst is Φ 8-22mm, height 5-10mm, the porous cylinder particulate catalytic
The surface area of agent/grain skeleton volume ratio is 0.8-1.3 mm2/mm3, radial maximum mass transfer distance is 1.4-3.0 mm, and side pressure is strong
Degree is 120-200 N/cm.
7. a kind of moulding process of special-shaped methanation catalyst according to claim 5, it is characterised in that the Ni-based first
The regular symmetrical porous cylinder beaded catalyst of geometry is made in the molding of Alkanizing catalyst powder by the way of extrusion；It is porous
Cylindrical particles catalyst profile circumscribed circle diameter is the surface of Φ 3-14mm, height 5-10mm, the porous cylinder beaded catalyst
Product/grain skeleton volume ratio is 1.0-1.6 mm2/mm3, radial maximum mass transfer distance is 1.8-4.0 mm, side pressure strength 80-
140 N/cm。
8. a kind of application of special-shaped methanation catalyst according to claim 1, it is characterised in that profile circumscribed circle diameter
It is 0.8-1.3 mm for Φ 8-22mm, height 5-10mm, surface area/grain skeleton volume ratio2/mm3, radial maximum mass transfer distance
For 1.4-3.0 mm, side pressure strength is the regular symmetrical porous gear column of the geometry of 120-200 N/cm or porous petal
The application conditions of columnar porous cylinder beaded catalyst are a large amount of methanations of CO that SNG processes are produced for synthesis gas methanation
Stage：Pressure is 1.0-5.0 MPa, temperature 280-700oC, volume space velocity is 20000-60000h-1、H2/(3CO +4CO2)
Molar ratio be 1.00-1.05, the CO+CO in raw material of synthetic gas gas2Contents on dry basis be 8-25 vol%.
9. a kind of application of special-shaped methanation catalyst according to claim 3, it is characterised in that profile circumscribed circle diameter
It is 1.0-1.6 mm for Φ 3-14mm, height 5-10mm, surface area/grain skeleton volume ratio2/mm3, radial maximum mass transfer distance
For 1.8-4.0 mm, side pressure strength is answering for the regular symmetrical porous cylinder beaded catalyst of the geometry of 80-140 N/cm
It is that the CO of SNG processes is produced for synthesis gas methanation with condition2Supplement the methanation stage：Pressure is 1.0-5.0 MPa, temperature
For 250-450oC, volume space velocity is 20000-60000h-1、H2/(3CO +4CO2) molar ratio be 0.80-1.00, synthesis gas
CO+CO in unstripped gas2Contents on dry basis be 3-8 vol%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0732146A1 (en) * | 1995-03-14 | 1996-09-18 | Montecatini Tecnologie S.R.L. | Catalysts and catalyst carriers obtained by tabletting |
| 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 |
| CN103127939A (en) * | 2011-11-24 | 2013-06-05 | 新奥科技发展有限公司 | Cellular integral sulfur-tolerant methanation catalyst and preparation method thereof |
| CN103706370A (en) * | 2013-12-17 | 2014-04-09 | 西南化工研究设计院有限公司 | High-temperature methanation catalyst for producing natural gas through coal and preparation method of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0732146A1 (en) * | 1995-03-14 | 1996-09-18 | Montecatini Tecnologie S.R.L. | Catalysts and catalyst carriers obtained by tabletting |
| 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 |
| CN103127939A (en) * | 2011-11-24 | 2013-06-05 | 新奥科技发展有限公司 | Cellular integral sulfur-tolerant methanation catalyst and preparation method thereof |
| CN103706370A (en) * | 2013-12-17 | 2014-04-09 | 西南化工研究设计院有限公司 | High-temperature methanation catalyst for producing natural gas through coal and preparation method of catalyst |
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