CN103691444B - A kind of novel high-temperature methanation catalyst and preparation method thereof - Google Patents
A kind of novel high-temperature methanation catalyst and preparation method thereof Download PDFInfo
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- CN103691444B CN103691444B CN201310694381.3A CN201310694381A CN103691444B CN 103691444 B CN103691444 B CN 103691444B CN 201310694381 A CN201310694381 A CN 201310694381A CN 103691444 B CN103691444 B CN 103691444B
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Abstract
The invention discloses a kind of novel high-temperature methanation catalyst and preparation method thereof, object is that the catalyst that solution synthetic natural gas processed adopts requires higher to heat-resisting, resistance to elevated temperatures, mainly rely on from external import at present, the problem that patent royalties are higher, this catalyst take nickel as active component, take cerium oxide as auxiliary agent, carrier is the mixture of aluminium oxide, silica, titanium oxide.Catalyst of the present invention has the features such as intensity is high, activity is good, Heat stability is good, anti-carbon nature are good, resistance to elevated temperatures is good, can meet heat-resisting, the high temperature resistant requirement of coal synthetic natural gas to catalyst.The present invention, for the cost reducing coal synthetic natural gas, solves the problem of natural gas supply deficiency, promotes that the development of coal preparing natural gas has great importance.
Description
Technical field
The present invention relates to chemical field, especially methanation catalyst field, be specially a kind of novel high-temperature methanation catalyst and preparation method thereof, it is mainly used in thinking raw material, preparation synthetic natural gas.
Background technology
Natural gas is as desirable clean energy resource, and have the advantages such as efficient, clean, transmission is convenient, its application is more and more extensive.Along with the quickening of urbanization process, and the raising day by day of living standards of the people, people are for the demand of natural gas, and in the impetus increased fast, larger breach then appears in natural gas supply.
The feature of China in the energy is rich coal, weak breath, oil-poor, and wherein coal reserves is very abundant.Therefore, to account for the proportion of energy one-time consumption higher in consumption of coal.Because the energy transformation ratio of coal preparing natural gas is high, water consumption is low, and offal treatment is relatively simple, and therefore, coal preparing natural gas has become coal Land use systems the most effective.For making full use of the coal resources of China's abundant, especially low-grade lignite resource, what the many places of China adopted is the approach that synthetic natural gas carries out supplying again prepared by coal.Which (coal synthetic natural gas) solves clean coal utilization, and solve one of effective measures of the not enough contradiction of natural gas supply.
The technological process adopting coal to prepare synthetic natural gas mainly comprises: coal gasification, Partial Transformation, gas purification and methanation four parts, wherein, synthesis gas methanation is the core of this technological process, and the key of synthesis gas methanation process is then the catalyst that methanation adopts.Prepare in the technique of synthetic natural gas at coal, the adiabatic temperature rise of methanation reaction is large, and this just proposes more strict requirement to heat-resisting, the resistance to elevated temperatures of catalyst.At present, high-temperature methanation catalyst technology provides primarily of foreign corporation, the rope company of Top of such as Denmark and the Dai Wei company of Britain.And domestic normal pressure portion of methane technology and trace amounts of CO, the CO only having production city coal gas at present of China
2deng the methanation catalyst of gas purification, at the catalyst there is no maturation in the high-temperature methanation of coal synthetic natural gas technique.In recent years, the domestic coal preparing natural gas project put into operation of China mainly still adopts external methanation technology, needs to pay huge patent royalties for this reason.Therefore, there is in the urgent need to exploitation the high-temperature methanation catalyst of independent intellectual property right.
Summary of the invention
Goal of the invention of the present invention is: the catalyst adopted for coal synthetic natural gas requires higher to heat-resisting, resistance to elevated temperatures, mainly rely on from external import at present, the problem that patent royalties are higher, provides a kind of novel high-temperature methanation catalyst and preparation method thereof.Catalyst of the present invention has the features such as intensity is high, activity is good, Heat stability is good, anti-carbon nature are good, resistance to elevated temperatures is good, can meet heat-resisting, the high temperature resistant requirement of coal synthetic natural gas to catalyst.The present invention, for the cost reducing coal synthetic natural gas, solves the problem of natural gas supply deficiency, promotes that the development of coal preparing natural gas has great importance.
To achieve these goals, the present invention adopts following technical scheme:
A novel high-temperature methanation catalyst is active component with nickel, take cerium oxide as auxiliary agent, and carrier is the mixture of aluminium oxide, silica, titanium oxide.
In this catalyst, the mass percent of each component is as follows:
NiO10%～20%，
Ce
2O
32%～10%，
Al
2O
325%～40%，
SiO
220%～30%，
TiO
220%～30%。
The preparation method of aforementioned novel high-temperature methanation catalyst, comprises the steps:
(1) take aluminium oxide, silica, titanium oxide, graphite by proportioning respectively, each component is mixed, finally by shaping for the mixture mixed, obtain shaped granule;
(2) shaped granule step 1 prepared is in 0.8MPa ~ 1.0MPa, the water vapor of 120 DEG C ~ 160 DEG C, and reaction 4h ~ 8h, obtains just base;
(3) first base is put into Muffle furnace, at 500 DEG C ~ 700 DEG C, calcining 4h ~ 6h, obtains catalyst carrier;
(4) get material liquid, catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C ~ 80 DEG C, constant temperature 0.5h ~ 1h, then takes out the catalyst carrier after heated at constant temperature, and catalyst carrier is put into baking oven, be heated to 110 DEG C ~ 130 DEG C, constant temperature 2h ~ 4h, obtains product;
In described step 1, aluminium oxide, silica, titanium oxide, graphite take by following ratio of weight and number:
Al
2o
330 ~ 50 parts,
SiO
225 ~ 35 parts,
TiO
225 ~ 35 parts,
4 parts, graphite;
In described step 4, material liquid is by Ni (NO
3)
26H
2o, Ce (NO
3)
36H
2o adds water formulated, containing 1170g ~ 2340gNi (NO in often liter of material liquid
3)
26H
2o, 150g ~ 760gCe (NO
3)
36H
2o.
In described step 1, the particle diameter of the aluminium oxide taken, silica, titanium oxide, graphite is less than 180 orders.
In described step 1, the aluminium oxide taken, silica, titanium oxide, graphite cross 200 mesh sieves.
In described step 1, by shaping according to the size of Φ 3.5mmx3.5mm for the mixture mixed, obtain shaped granule.
For foregoing problems, the invention provides a kind of novel high-temperature methanation catalyst and preparation method thereof.Catalyst of the present invention comprises carrier, active component and auxiliary agent three part, and wherein, carrier is aluminium oxide, silica and titanium oxide, and active component is nickel, and auxiliary agent is cerium oxide.The present invention with aluminium oxide, silica and titanium oxide for carrier, wherein, Al
2o
3cheap and easy to get, there is good structural form and surface property; SiO
2there is good pore structure, larger specific area; TiO
2belong to N-type semiconductor character, with load metal thereon, strong interaction can occur, thus affect absorption and the catalytic performance of catalyst, in addition, TiO
2surface there is the effects such as acid and chemical interactions.In the present invention adopt three kinds of materials to be prepared into complex carrier there is higher specific area, show higher catalytic activity after load active component, and increase active reaction temperature range.Meanwhile, in the present invention, take nickel as main active component; Take cerium oxide as auxiliary agent, adding of rare earth element can improve heat endurance and the acidity changing carrier surface.Active component nickel in the present invention is present in catalyst with the form of nickel oxide, and in catalyst of the present invention, the mass ratio of each component is as follows: 10% ~ 20%NiO, 2% ~ 10%Ce
2o
3, 25% ~ 40%Al
2o
3, 20% ~ 30%SiO
2, 20% ~ 30%TiO
2.
Meanwhile, the present invention also provides the preparation method of this catalyst, and the method comprises Kaolinite Preparation of Catalyst carrier, hydrothermal treatment consists, calcining, impregnating step.
Run under new type high temperature methanation catalyst prepared by the present invention is adapted at the condition of HTHP high-speed, and have that active high and low temperature activity is good, the advantage of the strong and high selectivity of high thermal stability, anti-agglutinatting property, there is the excellent properties such as conversion simultaneously, and production cost is low, the needs of industrialized mass production can be met.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is experimental provision schematic diagram.
Mark in figure: 1-1,1-2,1-3 are respectively flowmeter, 2-1,2-2 are voltage-stablizer, and 3 is devulcanizer, and 4 is evaporation mixer, and 5 is reactor, and 6 is water storing tank, and 7 is water pump, and 8 is cooling separator, and 9 is wet flow indicator, and 10 is transfer valve.
Detailed description of the invention
All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this description, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Embodiment 1
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 30gAl respectively
2o
3, 35gSiO
2, 35gTiO
2, then add 4g graphite, by Al
2o
3, SiO
2, TiO
2, graphite four kinds of components mix, then the mixture mixed is compressing by Φ 3.5mmx3.5mm size, obtains shaped granule.Shaped granule is put into still kettle, under 0.8MPa pressure, in 120 DEG C of water vapor, processes 8h, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, at 500 DEG C, calcines 6h, obtain catalyst carrier.
Take the Ni (NO of 585g respectively
3)
26H
2ce (the NO of O, 380g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C, constant temperature 1h, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 120 DEG C, constant temperature 2h, obtains finished catalyst.
Embodiment 2
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 35gAl respectively
2o
3, 30gSiO
2, 35gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 0.8MPa pressure, in 120 DEG C of water vapor, processes 6h, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, at 500 DEG C, calcines 6h, obtain catalyst carrier.
Take the Ni (NO of 819g respectively
3)
26H
2ce (the NO of O, 304g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 80 DEG C, constant temperature 0.5h, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 120 DEG C, constant temperature 2h, is finished catalyst.
Embodiment 3
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 35gAl respectively
2o
3, 30gSiO
2, 35gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 1.0MPa pressure, in 160 DEG C of water vapor, processes 4h, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, at 550 DEG C, calcines 4h, obtain catalyst carrier.
Take the Ni (NO of 819g respectively
3)
26H
2ce (the NO of O, 304g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C, constant temperature half an hour, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 130 DEG C, constant temperature 2h, is finished catalyst.
Embodiment 4
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take the Al of 40g respectively
2o
3, 30gSiO
2, 30gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 1.0MPa pressure, in 140 DEG C of water vapor, processes 4h, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, at 600 DEG C, calcines 4h, obtain catalyst carrier.
Take the Ni (NO of 936g respectively
3)
26H
2ce (the NO of O, 228g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 80 DEG C, constant temperature half an hour, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 130 DEG C, constant temperature 2h, is finished catalyst.
Embodiment 5
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 45gAl respectively
2o
3, 25gSiO
2, 30gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 1.0MPa pressure, in 160 DEG C of water vapor, processes 4h, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, calcines four hours at 600 DEG C, obtain catalyst carrier.
Take the Ni (NO of 1053g respectively
3)
26H
2ce (the NO of O, 152g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C, constant temperature half an hour, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 120 DEG C of constant temperature two hours, be finished catalyst.
Embodiment 6
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 50gAl respectively
2o
3, 25gSiO
2, 25gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 1.0MPa pressure, in 160 DEG C of water vapor, processes four hours, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, calcines four hours at 650 DEG C, obtain catalyst carrier.
Take the Ni (NO of 1170g respectively
3)
26H
2ce (the NO of O, 75g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C, constant temperature one hour, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 120 DEG C of constant temperature two hours, be finished catalyst.
Embodiment 7
Aluminium oxide, silica and titanium dioxide powder is levigate respectively, cross 200 mesh sieves for subsequent use.Take 50gAl respectively
2o
3, 25gSiO
2, 25gTiO
2, then add 4g graphite, these four kinds of components are mixed.Again by compressing by Φ 3.5mmx3.5mm size for the mixture mixed, obtain shaped granule.Shaped granule is put into still kettle, under 1.0MPa pressure, in 160 DEG C of water vapor, processes four hours, Temperature fall after taking out, obtain just base.First base is put into Muffle furnace, calcines four hours at 700 DEG C, be catalyst carrier.
Take the Ni (NO of 1170g respectively
3)
26H
2ce (the NO of O, 75g
3)
36H
2both are added water and are mixed with the material liquid of 500mL by O.Catalyst carrier is put into material liquid, then material liquid is heated to 80 DEG C, constant temperature half an hour, then the catalyst carrier after heated at constant temperature is taken out.Finally the catalyst carrier of taking out after heated at constant temperature in material liquid is put into baking oven, be heated to 120 DEG C of constant temperature two hours, be finished catalyst.
Catalyst prepared by the present invention is evaluated, relevant evaluation test and data as follows.
Get each 10mL of catalyst prepared by previous embodiment 1-7 respectively, be denoted as embodiment 1 respectively to embodiment 7.
Test method: reaction tube catalyst being loaded Φ 25 × 3.5cm, catalyst bed layer height is about 30mm, carries out determination of activity to catalyst.Determinator mainly comprises devulcanizer, evaporation mixer, high-temperature methanation adiabatic reactor.
Catalyst reduction condition: at temperature 400 DEG C, with hydrogen pressure-raising to 0.5MPa reductase 12 hour, reduction air speed 2000h
-1.
Catalyst runs condition: inlet temperature 300 DEG C, maximum temperature 630 DEG C, pressure 2.0MPa, steam-to-gas ratio 0.2, coal gas air speed 20000h
-1, carry out gas methanation reaction.
Select Agilent7820A chromatographic instrument, it has flame particle detector and thermal conductivity detector (TCD), and join filling and capillary column, carrier gas is argon gas, CO, CO in Main Analysis gas
2, CH
4, H
2.
Shown in raw material coal gas table 1 composed as follows, in table 1, the composition of component adopts percent by volume.
Table 1 determination of activity raw material coal gas composition (v%)
Catalyst measurement result is as shown in table 2.
Table 2 determination of activity result
As can be seen from the experimental data of above-described embodiment, catalyst of the present invention, under higher temperature (as 630 DEG C), still has higher activity and selectivity.
Above-mentioned experimental result also shows further: catalyst of the present invention runs under being adapted at the condition of HTHP high-speed, and have that active high and low temperature activity is good, the feature of the strong and high selectivity of high thermal stability, anti-agglutinatting property, also there is the excellent properties such as conversion.And the preparation method of catalyst of the present invention is simple, production cost is low, is suitable for large-scale promotion application.
The present invention is not limited to aforesaid detailed description of the invention.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (5)
1. a high-temperature methanation catalyst, is characterized in that, is active component with nickel, take cerium oxide as auxiliary agent, and carrier is the mixture of aluminium oxide, silica, titanium oxide;
In this catalyst, the mass percent of each component is as follows:
NiO10%～20%，
Ce
2O
32%～10%，
Al
2O
325%～40%，
SiO
220%～30%，
TiO
220%～30%。
2. the preparation method of high-temperature methanation catalyst according to claim 1, is characterized in that, comprise the steps:
(1) take aluminium oxide, silica, titanium oxide, graphite by proportioning respectively, each component is mixed, finally by shaping for the mixture mixed, obtain shaped granule;
(2) shaped granule step (1) prepared is in 0.8MPa ~ 1.0MPa, the water vapor of 120 DEG C ~ 160 DEG C, and reaction 4h ~ 8h, obtains just base;
(3) first base is put into Muffle furnace, at 500 DEG C ~ 700 DEG C, calcining 4h ~ 6h, obtains catalyst carrier;
(4) get material liquid, catalyst carrier is put into material liquid, then material liquid is heated to 70 DEG C ~ 80 DEG C, constant temperature 0.5h ~ 1h, then takes out the catalyst carrier after heated at constant temperature, and catalyst carrier is put into baking oven, be heated to 110 DEG C ~ 130 DEG C, constant temperature 2h ~ 4h, obtains product;
In described step (1), aluminium oxide, silica, titanium oxide, graphite take by following ratio of weight and number:
Al
2o
330 ~ 50 parts,
SiO
225 ~ 35 parts,
TiO
225 ~ 35 parts,
4 parts, graphite;
In described step (4), material liquid is by Ni (NO
3)
26H
2o, Ce (NO
3)
36H
2o adds water formulated, containing 1170g ~ 2340gNi (NO in often liter of material liquid
3)
26H
2o, 150g ~ 760gCe (NO
3)
36H
2o.
3. the preparation method of high-temperature methanation catalyst according to claim 2, it is characterized in that, in described step (1), the particle diameter of the aluminium oxide taken, silica, titanium oxide, graphite is less than 180 orders.
4. the preparation method of high-temperature methanation catalyst according to claim 3, it is characterized in that, in described step (1), the aluminium oxide taken, silica, titanium oxide, graphite cross 200 mesh sieves.
5. the preparation method of high-temperature methanation catalyst according to claim 2, is characterized in that, in described step (1), by shaping according to the size of Φ 3.5mmx3.5mm for the mixture mixed, obtain shaped granule.
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Citations (4)
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|---|---|---|---|---|
| US4847231A (en) * | 1988-06-08 | 1989-07-11 | Gas Research Institute | Mixed ruthenium catalyst |
| CN101703933A (en) * | 2009-11-06 | 2010-05-12 | 山西大学 | Bimetal methanation catalyst and preparation method thereof |
| CN102500379A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for methanation and preparation method thereof |
| CN102527405A (en) * | 2012-02-15 | 2012-07-04 | 华东理工大学 | Catalyst used in complete methanation of synthesis gas at high temperature and preparation method thereof |
-
2013
- 2013-12-18 CN CN201310694381.3A patent/CN103691444B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847231A (en) * | 1988-06-08 | 1989-07-11 | Gas Research Institute | Mixed ruthenium catalyst |
| CN101703933A (en) * | 2009-11-06 | 2010-05-12 | 山西大学 | Bimetal methanation catalyst and preparation method thereof |
| CN102500379A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for methanation and preparation method thereof |
| CN102527405A (en) * | 2012-02-15 | 2012-07-04 | 华东理工大学 | Catalyst used in complete methanation of synthesis gas at high temperature and preparation method thereof |
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