CN102416328B - Catalyst for preparing synthesis gases through methane carbon dioxide reforming (DMR) and preparation method thereof - Google Patents
Catalyst for preparing synthesis gases through methane carbon dioxide reforming (DMR) and preparation method thereof Download PDFInfo
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Abstract
The invention provides a catalyst for preparing synthesis gases through dry methane reforming (DMR) and a preparation method thereof, belonging to the technical field of catalysts for preparing synthesis gases through DMR. The catalyst is formed by nickel, iron, cerium oxide and magnesia-alumina spinel. The method comprises the following steps of: firstly preparing a mesoporous MgAl2O4 spinel carrier, then preparing a nickel-based catalyst suspension and finally preparing the finished product through such simple processes as filtering, washing, drying and roasting. The catalyst and the preparation method have the following beneficial effects that: as such non-precious metal raw materials as nickel and iron are adopted and the raw material sources are wide, the cost is low; the process is simple, the equipment is simple and the production cost is low; the prepared product has high catalytic activity; the conversion rates of methane and carbon dioxide are high; and the carbon depositionresistance and stability are good. The catalyst can be widely used for preparing synthesis gases through DMR.
Description
Technical field
The invention belongs to the catalyst technical field for synthesizing gas by reforming methane with co 2, be specifically related to nickel-base catalyst of synthesizing gas by reforming methane with co 2 and preparation method thereof.
Technical background
The several methods such as methane portion oxidation (POM) commonly used, methane vapor reforming (SRM), methane carbon dioxide reformation (DMR) take methane as the waste synthesis gas.Wherein methane carbon dioxide reformation is a strong endothermic process, and reaction equation is as follows:
CH
4+CO
2＝2H
2+2CO
The ratio of hydrogen and carbon monoxide is 1 in theory in the synthesis gas (hydrogen and carbon monoxide) that this reaction produces, and synthesis gas is the desirable feedstock of the liquid fuels such as the synthetic preparation of Fischer-Tropsch diesel oil, paraffin, also is the important source material of preparation methyl alcohol and dimethyl ether.Methyl alcohol itself also can be used as motor vehicle fuel to methyl alcohol for the synthesis of products such as fiber, plastics, agricultural chemicals, dyestuffs industrial, and dimethyl ether can be used as a kind of cold-producing medium and domestic fuel.The more important thing is, carbon dioxide and methane are two kinds of greenhouse gases that earth environment is had the greatest impact, methane carbon dioxide reformation utilizes the two to produce useful synthesis gas simultaneously can effectively reduce greenhouse gas emission, improves the global climate disaster of bringing because of greenhouse gases.The methane carbon dioxide reformation process is specially adapted to be rich in CO simultaneously
2Gas field, reduced separation of C O
2The expense of bringing.Therefore; synthesizing gas by reforming methane with co 2 has higher scientific meaning and practical value to the utilization of resources and environmental protection; be subject in recent years the more and more higher attention of people, some enterprise has realized that methane and carbon dioxide and steam unites the commercial Application that transforms preparing synthetic gas.
Noble metal take Pt, Pd as representative and all methane reforming with carbon dioxide is had activity take Ni, Co, Fe as the VII metalloid of representative, but because of the noble metals such as Pt, Pd expensive, and Ni has the catalytic activity suitable with noble metals such as Pt, Pd, thereby the research of methane reforming with carbon dioxide catalyst is concentrated in the catalyst based research of Ni.The problem that faces is that Ni is catalyst based very easily because carbon deposit loses activity, thereby causes the obstruction of reactor.Thereby to develop the good Ni of anti-Coking Behavior catalyst based be the key of methane reforming with carbon dioxide.
Nickel-base catalyst of existing synthesizing gas by reforming methane with co 2 and preparation method thereof is 200810117478.7 " a kind of methane-CO 2 reformation prepares its preparation method of synthetic gas catalyst " such as application number, and the mass fraction of disclosed catalyst is:
Nickel 5～20%
Cerium oxide base composite assistant 0.1～5%
Platinum 0.01～1%
All the other are that carrier (is γ-Al
2O
3, NiAl
2O
4In one or both)
Wherein nickel derives from soluble nickel salt, and other components that contain in the cerium oxide base composite assistant are one or both in lanthana, the titanium oxide, the mol ratio 5/1～1/5 of cerium oxide and other oxides.The preparation method of disclosed catalyst is: prepare first modified support (A), again (A) be impregnated in the soluble nickel salting liquid, or (A) be impregnated in the platinum acid chloride solution, drying and roasting obtain (B) or (C), then sample (B) be impregnated in the platinum acid chloride solution, or sample (C) be impregnated in the soluble nickel salting liquid, drying and roasting obtain catalyst precursor, at last aforesaid presoma are reduced in the hydrogen helium gas mixture and make finished product.The major defect of this patent is: the 1. raw materials used noble metal that contains, cost is high, is not suitable for large-scale production.2. this catalyst is applied to low conversion rate in the reaction, and active low, the carbon deposit situation is serious.3. the crystal structure of the catalyst of this preparation method's preparation is difficult to control, and specific area is low, and the dispersion effect of reactive metal is poor.
Summary of the invention
The objective of the invention is the weak point for nickel-base catalyst that has synthesizing gas by reforming methane with co 2 now and preparation method thereof, bimetallic catalyst of a kind of synthesizing gas by reforming methane with co 2 and preparation method thereof is provided.This catalyst has that specific surface height, reactive metal good dispersion and anti-carbon performance are good, catalytic activity and stability is high, the preparation method is simple, and cost is low, and raw material is the characteristics such as acquisition easily.
Mechanism of the present invention: the MgAl that the present invention adopts
2O
4The spinelle mesoporous material has the advantages that specific area is large, the aperture is relatively large, thereby is conducive to improve load capacity and the decentralization of reactive metal as the carrier of catalyst.The present invention at first with the gel-sol legal system standby a kind of MgAl with meso-hole structure
2O
4Then spinelle has prepared Ni/Fe/CeO with urea deposits-precipitation method
2/ MgAl
2O
4Catalyst based, the catalyst activity metal grain particle diameter of the method preparation is little, particle diameter is evenly distributed, and with carrier stronger interaction is arranged.Thereby catalyst has good anti-Coking Behavior and catalytic activity and stability.And CeO
2Adding can improve the transfer ability of oxygen in the catalyst, the simultaneously adding of the second active component Fe can be brought into play the synergy of Ni and Fe, wherein Ni can promote the reduction of Fe, and Fe can improve catalyst to CO
2Adsorption capacity, thereby can suppress the generation of low activity carbon species, further promote the anti-carbon performance of catalyst.
The technical scheme that realizes the object of the invention is: a kind of component and mass fraction thereof of catalyst of synthesizing gas by reforming methane with co 2 are as follows:
A kind of preparation method of catalyst of synthesizing gas by reforming methane with co 2 prepares first mesoporous MgAl
2O
4Spinel carrier prepares nickel-base catalyst suspension again, makes finished product finally by filtration, washing, simple process dry, roasting.Its concrete grammar step is as follows:
(1) prepares mesoporous MgAl
2O
4Spinel carrier
First in the mole (mol) of magnesium nitrate: the mole of aluminum nitrate (mol): the ratio of the volume of distilled water (ml) is 1: 1.7～2.3: 1000～1500 ratio, magnesium nitrate and aluminum nitrate are joined in the distilled water, be stirred to and make the A mixed liquor till the dissolving.Again in the mole (mol) of softex kw: the volume of citric acid (ml): the ratio of the volume of ethylene glycol (ml) is 1: 2000～2500: 200～400 ratio, under stirring condition, first softex kw and citric acid are mixed, rear adding ethylene glycol mixes makes the B mixed liquor.Then with after A mixed liquor and the B mixed liquor mixing and stirring, be positioned in the thermostatical water bath, till being stirred to the formation gel under 70～80 ℃ of conditions.Again gelling material is positioned in the drying box, lower dry 45～55 hours at 110～130 ℃.It is last at last dry thing to be pulverized by grinder, is positioned in the Muffle furnace, 680～720 ℃ of lower calcinings 5～6 hours, namely prepares mesoporous MgAl
2O
4Spinel carrier.
(2) preparation nickel-base catalyst suspension
(1) step finish after, first in nickel nitrate: ferric nitrate: ammonium ceric nitrate: urea: the ratio of the mole of nitric acid (mol) is 1: 0.2～1: 0.5～1: 1～1.5: 0.1～0.3 ratio, and nickel nitrate, ferric nitrate, ammonium ceric nitrate, urea and nitric acid mixing and stirring are prepared into mixed liquor C.Again by the mesoporous MgAl for preparing in (1) step
2O
4The quality of spinel carrier (g): the ratio of the volume of mixed liquor C (ml) is 1: 100～130 ratio, with mesoporous MgAl
2O
4Spinel carrier joins among the mixed liquor C after the mixing and stirring, is positioned in the thermostatical water bath, 85～95 ℃ of lower stirrings 2.5～3.5 hours, then is cooled to rapidly room temperature, makes nickel-base catalyst suspension.
(3) preparation nickel-base catalyst finished product
(2) step went on foot the suspension that makes with (2) first and filters with filter plant after finishing, and collected respectively filtrate and filter residue.The treated rear discharging up to standard of filtrate of collecting; To the filter residue of collecting, make washing agent with distilled water, in the quality (g) of filter residue: the ratio of the volume of distilled water washing agent (ml) is 1: 30～50 ratio, uses the distilled water flushing filter residue, collects respectively scrub raffinate and washed-residue.The treated rear discharging up to standard of scrub raffinate of collecting; To the washed-residue of collecting, make washing agent with distilled water again, again in the quality (g) of washed-residue: the ratio of the volume of distilled water washing agent (ml) is 1: 30～50 ratio, again with distilled water washed-residue is washed.So repeated washing is 3～5 times, just makes catalyst precursor.Then the catalyst precursor that makes is put in the drying box, lower dry 24～26 hours at 100～110 ℃.At last dry thing is positioned in the Muffle furnace, 600～610 ℃ of lower roastings 8～9 hours, just prepares nickel-base catalyst product of the present invention.
After the present invention adopts technique scheme, mainly contain following effect:
1. methane and CO
2Conversion ratio high.In that prepared catalyst reduces behind the 4h online to the present invention on the catalyst on-line evaluation device, then carry out online reaction detection, at CH
4/ CO
2Volume ratio is 1,700 ℃ of reaction temperatures, and normal pressure, gas space velocity is 2500h
-1, the conversion ratio of methane is up to 87%, and the conversion ratio of carbon dioxide is also up to 87%.
2. anti-Coking Behavior and good stability.The prepared catalyst of the present invention is after reaction 72 hours, and catalytic activity does not obviously reduce.
3. raw material sources are wide, and cost is low.The present invention all adopts the base metal raw materials such as Ni, Fe, and wide material sources greatly reduce cost;
4. preparation section is simple, and output is large.Catalyst can use commercially available MgAl
2O
4Spinelle is carrier, adopts above-mentioned deposition-precipitation method preparation, and technique is simple;
5. equipment is simple, invests little.The inventive method has only been used the instrument simply commonly used such as constant temperature water bath, drying box, Muffle furnace, if be applied to industrial production, only needs simple water bath with thermostatic control and firing equipment, invests littlely, is convenient to utilization and extention.
The present invention can be widely used as the catalyst of synthesizing gas by reforming methane with co 2.And the preparation method who adopts has also broken traditional preparation method's pattern.
The specific embodiment
Below in conjunction with the specific embodiment, further specify the present invention.
Embodiment 1
A kind of component of catalyst of synthesizing gas by reforming methane with co 2 and mass percent thereof are:
A kind of preparation method's of catalyst of synthesizing gas by reforming methane with co 2 concrete steps are as follows:
(1) prepares mesoporous MgAl
2O
4Spinel carrier
First in the mole (mol) of magnesium nitrate: the mole of aluminum nitrate (mol): the ratio of the volume of distilled water (ml) is 1: 2: 1300 ratio, magnesium nitrate and aluminum nitrate are joined in the distilled water, be stirred to and make the A mixed liquor till the dissolving.Again in the mole (mol) of softex kw: the volume of citric acid (ml): the ratio of the volume of ethylene glycol (ml) is 1: 2300: 300 ratio, under stirring condition, first softex kw and citric acid are mixed, rear adding ethylene glycol mixes makes the B mixed liquor.Then with after A mixed liquor and the B mixed liquor mixing and stirring, be positioned in the thermostatical water bath, till being stirred to the formation gel under 75 ℃ of conditions.Again gelling material is positioned in the drying box, lower dry 50 hours at 120 ℃.It is last at last dry thing to be pulverized by grinder, is positioned in the Muffle furnace, 700 ℃ of lower calcinings 6 hours, namely prepares mesoporous MgAl
2O
4Spinel carrier.
(2) preparation nickel-base catalyst suspension
(1) step finish after, first in nickel nitrate: ferric nitrate: ammonium ceric nitrate: urea: the ratio of the mole of nitric acid (mol) is 1: 0.6: 0.7: 1.3: 0.2 ratio is prepared into mixed liquor C with nickel nitrate, ferric nitrate, ammonium ceric nitrate, urea and nitric acid mixing and stirring.Again by the mesoporous MgAl for preparing in (1) step
2O
4The quality of spinel carrier (g): the ratio of the volume of mixed liquor C (ml) is 1: 120 ratio, with mesoporous MgAl
2O
4Spinel carrier joins among the mixed liquor C after the mixing and stirring, is positioned in the thermostatical water bath, 90 ℃ of lower stirrings 3 hours, then is cooled to rapidly room temperature, makes nickel-base catalyst suspension.
(3) preparation nickel-base catalyst finished product
(2) step went on foot the suspension that makes with (2) first and filters with filter plant after finishing, and collected respectively filtrate and filter residue.The treated rear discharging up to standard of filtrate of collecting; To the filter residue of collecting, make washing agent with distilled water, in the quality (g) of filter residue: the ratio of the volume of distilled water washing agent (ml) is 1: 40 ratio, uses the distilled water flushing filter residue, collects respectively scrub raffinate and washed-residue.The treated rear discharging up to standard of scrub raffinate of collecting; To the washed-residue of collecting, make washing agent with distilled water again, again in the quality (g) of washed-residue: the ratio of the volume of distilled water washing agent (ml) is 1: 40 ratio, again with distilled water washed-residue is washed, so repeated washing is 4 times, just makes catalyst precursor.Then catalyst precursor is put in the drying box, lower dry 25 hours at 105 ℃.At last dry thing is positioned in the Muffle furnace, 605 ℃ of lower roastings 8.5 hours, just prepares nickel-base catalyst product of the present invention.
Embodiment 2
A kind of component of catalyst of synthesizing gas by reforming methane with co 2 and mass percent thereof are:
A kind of preparation method of catalyst of synthesizing gas by reforming methane with co 2, with embodiment 1, wherein:
In (1) step, mixed liquor A is by the mole (mol) of magnesium nitrate: the mole of aluminum nitrate (mol): the ratio of the volume of distilled water (ml) is that 1: 1.7: 1000 ratio is made into.Mixed liquid B is by the mole (mol) of softex kw: the volume of citric acid (ml): the ratio of the volume of ethylene glycol (ml) is that 1: 2000: 200 ratio is made into.Temperature in the thermostatical water bath is 80 ℃.Temperature in the drying box is 130 ℃, and be 45 hours drying time.Calcining heat in the Muffle furnace is 680 ℃, and calcination time is 5.5 hours.
In (2) step, mixed liquor C is by nickel nitrate: ferric nitrate: ammonium ceric nitrate: urea: the ratio of the mole of nitric acid (mol) is 1: 0.2: 1: 1.5: 0.1 ratio is made into.Nickel-base catalyst suspension is by the mesoporous MgAl for preparing in (1) step
2O
4The quality of spinel carrier (g): the ratio of the volume of mixed liquor C (ml) is that 1: 100 ratio is made into.Temperature in the thermostatical water bath is 85 ℃, and mixing time is 3.5 hours.
In (3) step, the quality of filter residue (g): the ratio of the volume of distilled water washing agent (ml) is 1: 30.The quality of washed-residue (g): the ratio of the volume of distilled water washing agent (ml) is 1: 30, repeated washing 5 times.Temperature in the drying box is 100 ℃, and be 26 hours drying time.Sintering temperature in the Muffle furnace is 610 ℃, and roasting time is 8 hours.
Embodiment 3
A kind of component of catalyst of synthesizing gas by reforming methane with co 2 and mass percent thereof are:
A kind of preparation method of catalyst of synthesizing gas by reforming methane with co 2, with embodiment 1, wherein:
In (1) step, mixed liquor A is by the mole (mol) of magnesium nitrate: the mole of aluminum nitrate (mol): the ratio of the volume of distilled water (ml) is that 1: 2.3: 1500 ratio is made into.Mixed liquid B is by the mole (mol) of softex kw: the volume of citric acid (ml): the ratio of the volume of ethylene glycol (ml) is that 1: 2500: 400 ratio is made into.Temperature in the thermostatical water bath is 70 ℃.Temperature in the drying box is 110 ℃, and be 55 hours drying time.Calcining heat in the Muffle furnace is 720 ℃, and calcination time is 5 hours.
In (2) step, mixed liquor C is by nickel nitrate: ferric nitrate: ammonium ceric nitrate: urea: the ratio of the mole of nitric acid (mol) is 1: 1: 0.5: 1: 0.3 ratio is made into, and nickel-base catalyst suspension is by the mesoporous MgAl for preparing in (1) step
2O
4The quality of spinel carrier (g): the ratio of the volume of mixed liquor C (ml) is that 1: 130 ratio is made into, and the temperature in the thermostatical water bath is 95 ℃, and mixing time is 2.5 hours.
In (3) step, the quality of filter residue (g): the ratio of the volume of distilled water washing agent (ml) is 1: 50.The quality of washed-residue (g): the ratio of the volume of distilled water washing agent (ml) is 1: 50, repeated washing 3 times.Temperature in the drying box is 110 ℃, and be 24 hours drying time.Sintering temperature in the Muffle furnace is 600 ℃, and roasting time is 9 hours.
Experimental result
To catalyst of the present invention, at different Ni and Fe and CeO
2Under the content, with the catalyst prod that the inventive method is prepared, carry out the result of active testing, as shown in table 1.
The activity of the catalyst of table 1 different component content
To the catalytic component of present embodiment 1, the catalyst prod that the preparation method of employing embodiment 1 prepares, the result who carries out anti-Coking Behavior test, as shown in table 2.
Table 2Ni content 9.8%, Fe content 5.8%, CeO
2The bimetallic Ni-Fe/Ce/MgO-Al of content 5.3%
2O
3Catalyst anti-carbon performance
From above-mentioned result of the test as can be known:
(1) as can be seen from Table 1, all up to more than 87%, catalytic efficiency is better for the conversion ratio under various catalyst, so the present invention can be applied to the Catalysts and its preparation method of synthesizing gas by reforming methane with co 2 preferably;
(2) as can be seen from Table 1, when Ni content be that 9.8%, Fe content is 5.8%, CeO
2Content is 5.3%, bimetallic Ni-Fe/Ce/MgO-Al
2O
3The conversion ratio of catalyst and selection rate are the highest, and it is active best, along with Ni, Fe and CeO
2Content increase or reduce, its conversion ratio and selection rate all decrease;
(3) as can be seen from Table 2, in the course of reaction, prolongation in time, methane conversion descends slowly, illustrates that thus the stability of catalyst of the present invention and anti-carbon performance are good.
Claims (1)
1. the preparation method of the catalyst of a synthesizing gas by reforming methane with co 2 is characterized in that its concrete grammar step is as follows:
(1) prepares mesoporous MgAl
2O
4Spinel carrier
First in the mole of magnesium nitrate: the mole of aluminum nitrate: the ratio of the volume of distilled water is the ratio of 1mol: 1.7～2.3mol: 1000～1500ml, magnesium nitrate and aluminum nitrate are joined in the distilled water, be stirred to and make the A mixed liquor till the dissolving, again in the mole of softex kw: the volume of citric acid: the ratio of the volume of ethylene glycol is the ratio of 1mol: 2000～2500ml: 200～400ml, under stirring condition, first softex kw and citric acid are mixed, rear adding ethylene glycol mixes makes the B mixed liquor, then with after A mixed liquor and the B mixed liquor mixing and stirring, be positioned in the thermostatical water bath, till being stirred to the formation gel under 70～80 ℃ of conditions, again gelling material is positioned in the drying box, lower dry 45～55 hours at 110～130 ℃, pulverize dry thing last by grinder at last, be positioned in the Muffle furnace, 680～720 ℃ of lower calcinings 5～6 hours;
(2) preparation nickel-base catalyst suspension
(1) step finish after, first in nickel nitrate: ferric nitrate: ammonium ceric nitrate: urea: the ratio of the mole of nitric acid is 1: 0.2～1: 0.5～1: 1～1.5: 0.1～0.3 ratio, nickel nitrate, ferric nitrate, ammonium ceric nitrate, urea and nitric acid mixing and stirring are prepared into mixed liquor C, again by the mesoporous MgAl for preparing in (1) step
2O
4The quality of spinel carrier: the ratio of the volume of mixed liquor C is the ratio of 1g: 100～130ml, with mesoporous MgAl
2O
4Spinel carrier joins among the mixed liquor C after the mixing and stirring, is positioned in the thermostatical water bath, 85～95 ℃ of lower stirrings 2.5～3.5 hours, then is cooled to rapidly room temperature;
(3) preparation nickel-base catalyst finished product
(2) step finish after, the suspension that first (2) step was made filters with filter plant, collect respectively filtrate and filter residue, to the filter residue of collecting, make washing agent with distilled water, quality in filter residue: the ratio of the volume of distilled water washing agent is the ratio of 1g: 30～50ml, use the distilled water flushing filter residue, collect respectively scrub raffinate and washed-residue, to the washed-residue of collecting, make washing agent with distilled water again, again in the quality of washed-residue: the ratio of the volume of distilled water washing agent is the ratio of 1g: 30～50ml, again with distilled water washed-residue is washed, so repeated washing 3～5 times and make catalyst precursor, then the catalyst precursor that makes is put in the drying box, drying is 24～26 hours under 100～110 ℃, at last dry thing is positioned in the Muffle furnace, 600～610 ℃ of lower roastings 8～9 hours, just prepare the nickel-base catalyst finished product, component and the mass percent thereof of described catalyst are as follows:
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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 |
| CN101703933A (en) * | 2009-11-06 | 2010-05-12 | 山西大学 | Bimetal methanation catalyst and preparation method thereof |
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
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