CN104955564A - Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same - Google Patents

Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same Download PDF

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CN104955564A
CN104955564A CN201380071806.3A CN201380071806A CN104955564A CN 104955564 A CN104955564 A CN 104955564A CN 201380071806 A CN201380071806 A CN 201380071806A CN 104955564 A CN104955564 A CN 104955564A
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catalyst
reforming catalyst
steam
lanthanum
reforming
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郑钟台
牟镛骐
李智惠
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Korea Gas Corp
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    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract

The present invention relates to a catalyst for manufacturing a synthetic gas from a natural gas by using carbon dioxide, and more specifically, to a catalyst useful for manufacturing a synthetic gas by means of steam-carbon dioxide reforming. The catalyst according to the present invention is manufactured by a method comprising the steps of: 1) manufacturing a zirconia and alumina support coated with lanthanum and cerium by wet or dry ball milling; and 2) mixing and firing a powder of the support in step 1) and a nickel powder. The ratio of hydrogen to carbon monoxide in the synthetic gas, which is manufactured by using the catalyst according to the present invention, can be controlled to 2.0+-0.2, thereby easily providing the synthetic gas which is efficient for producing synthetic petrochemical products (such as wax, naphtha, and diesel).

Description

For being manufactured containing lanthanum catalyst and using it to manufacture the method for synthesis gas of synthesis gas by steam-CO 2 reformation
Technical field
The present invention relates to the catalyst for being produced synthesis gas by natural gas by use carbon dioxide.More specifically, the present invention relates to the method containing lanthanum catalyst and this catalyst of preparation that can be used for being produced synthesis gas by steam-CO 2 reformation (SCR).
Background technology
Industrially used for using catalyst and oxidant from the reforming process of the so-called synthesis gas of key component methane production (mixture of hydrogen and carbon monoxide) of natural gas and become basic process important in chemical industry.
The synthesis gas produced by reforming methane is formed the basis of C1 chemistry and is applied to the production of methyl alcohol, hydrogen, ammonia etc.In recent years, become based on synthesis gas production production fluid fluid fuel in next life and oxygenatedchemicals the important channel utilizing natural gas.
By oxidant as oxygen, steam (steam), carbon dioxide and their mist be used for produce synthesis gas by hydrocarbon.According to the kind of oxidant, large quantifier elimination is carried out to the development of the catalyst with different qualities.
For comprising steam reforming, CO 2 reformation, partial oxidative steam reforming, self-heating recapitalization, tri-reforming and other reforming reactions by the reforming process of methane production synthesis gas.
Steam reforming reaction is according to the generation described in scheme 1.
scheme 1
CH 4+H 2O→CO+3H 2，ΔH 298＝+206kJ/mol
For this reason, mainly nickel-base catalyst is used.In steam reforming process, think because the inactivation of Carbon deposition reforming catalyst is sixty-four dollar question.Can by hydrogen atom in product and the mol ratio of carbon atom and the molar specific heat Mechanics Calculation Carbon deposition of oxygen atom and carbon atom.Therefore, for preventing catalyst from causing the object of inactivation by Carbon deposition, in the process of steam reforming methane, add excessive steam with the mol ratio of the mol ratio and oxygen atom and carbon atom that increase hydrogen atom and carbon atom.Therefore, water relative lifting, and thus obtain the synthesis gas with the hydrogen of 3 or higher and the mol ratio of carbon monoxide.This is applicable to the ammonia production process of the hydrogen needing high-load and the synthesis gas process for the production of high concentration hydrogen.The steam reforming process of the methane of current industrial application carries out with the methane of 1:4-6 and steam mol ratio under the pressure of the temperature of 730 to 860 DEG C and 20 to 40atm.
Most steam reforming reaction uses nickel-base catalyst.But nickel-base catalyst is due to the life-span [S.H.Lee, W.C.Cho, W.S.Ju, B.H.Cho, Y.C.Lee, Y.S.Baek, Catal.Today 84 (2003) 133] of the inactivation shortening catalyst of Carbon deposition.Therefore, there are the needs that development has the reforming catalyst of the performance being better than conventional steam reforming catalyst.For commercial Application, require that this reforming catalyst has good heat and mechanical stability and high resistance to cokeability.In order to meet these requirements, selecting suitable carrier, as alpha-alumina supports, is very crucial for steam reforming catalyst.
Load some catalyst on zirconia are known steam reforming catalyst.Such as, U.S. Patent number 4,026,823 (1975) nickel-Co catalysts disclosing the zirconia load of the steam reforming catalyst as hydrocarbon.In addition, U.S. Patent number 4,060,498 disclose the catalyst comprising Raney nickel, co-catalyst and general carrier, wherein, co-catalyst is metal as the mixture of lanthanum or cerium, and silver is added in Raney nickel with suitable ratio, and load is on carrier, and carrier is aluminium oxide, silica, magnesia or zirconia.In addition, U.S. Patent number 4,297,205 (1980) and 4,240,934 (1978) steam reforming catalyst disclosing hydrocarbon, wherein, iridium load is on zirconia/alumina support.But these catalyst suffer active reduction or inactivation under high-speed when being applied to steam reforming reaction.Therefore, for for steam reforming reaction, need modified zirconia to keep catalyst activity in the reaction, catalyst stability at high temperature and the activity of catalyst under high gas space velocity.
In this respect, Korean patent No. 10-0394076 (exercise question is " for the production of the Ni-based reforming catalyst of synthesis gas with for using it by the method for steam reforming by natural gas production synthesis gas ") proposes the Ni-based reforming catalyst (Ni/Ce-Zr for the production of synthesis gas 2), it comprises cerium modified Zirconia carrier and the nickel of load on carrier, and wherein, the amount of nickel is by weight 5% to 20% and the amount of cerium is every moles zirconium 0.01 to 1.0 mole.Also use dipping or melting process by Ni Kaolinite Preparation of Catalyst on carrier with cerium modified Zirconia carrier alternatively by using co-precipitation or sol-gel process preparation.
On the other hand, the generation described according to scheme 2 of the CO 2 reforming reaction of methane.
scheme 2
CH 4+CO 2→2CO+2H 2，ΔH 298＝+247.3kJ/mol
As in the steam reforming reaction of methane, mainly nickel-base catalyst is used for the CO 2 reforming reaction of methane.Alternately, noble metal-based catalysts can be used.Due to very a large amount of carbon monoxide (H 2: CO=1:1) existence, can adopt by use carbon dioxide methane reforming reaction produce synthesis gas for the production of dimethyl ether (dimethyl ester, DME).But Carbon deposition causes catalyst serious inactivation.Given this, the noble metal-based catalysts of the problem that suggestion is not relevant to Carbon deposition.Such as, at U.S. Patent number 5,068, known Pt/Al in 057 2o 3and Pd/Al 2o 3catalyst.International Patent Publication No. WO 92/11,199 proposes the aluminium oxide catalyst of noble metal (such as, iridium, rhodium and the ruthenium) load showing the strong active life-span with extending.Noble metal-based catalysts is that highly resistance to Carbon deposition is also very active compared with nickel-base catalyst, but is not suitable for industrial use due to their high price.
Therefore, lasting effort is made to develop the Carbon deposition minimized in the steam-CO 2 reforming reaction of methane and the catalyst can prepared with the cost reduced, to promote their commercial Application.
Summary of the invention
Technical problem
The present invention aims to provide the Ni-based reforming catalyst for being produced synthesis gas or hydrogen with high yield by steam-CO 2 reformation, and it has superior activity and stability to prevent from forming by coke the catalysqt deactivation caused maintenance is long-life simultaneously.
The solution of problem
One aspect of the present invention is provided for the reforming catalyst producing synthesis gas, and it is by comprising following method preparation:
1) by wet-mixing or dry ball milling preparation lanthanum and cerium modified zirconia/alumina support; And
2) blend step 1) in the support powder of preparation and nickel by powder calcining mixt.
Another aspect of the present invention is provided for using catalyst to produce the method for synthesis gas by steam-CO 2 reformation.
Advantageous effects of the present invention
Catalyst of the present invention minimizes to be produced Carbon deposition in synthesis gas process by the steam-CO 2 reformation (SCR) of methane and can be produced has H 2the synthesis gas of/CO ratio (2.0 ± 0.2), it is effective in the manufacture of petroleum chemicals (such as, wax, naphtha and diesel oil).Therefore, this catalyst is used to contribute to reducing the production cost of synthesis gas and the manufacturing cost of petroleum chemicals.And the process of this catalyst can be used to be applied to dimethyl ether (DME) Floating Production, storage and emptying (FPSO) system and gas-liquid GTL (gas to liquid) FPSO (Floating Production stores and emptying) system by catalyst of the present invention.Therefore, expect to find the application of the present invention in multiple industrial circle.
Accompanying drawing explanation
The figure of the mol ratio between the hydrogen of the synthesis gas that Fig. 1 produces under showing the condition being formed in and specifying in embodiment 1 and 6 and carbon monoxide.
Fig. 2 is the figure produced under the condition of specifying in embodiment 1 and 6 is shown from the conversion ratio of the methane of natural gas in the process of synthesis gas.
Detailed description of the invention
The present invention relates to the nickel of the relatively resistance to Carbon deposition of use and the Ni-based steam reforming catalyst of lanthanide series.
Particularly, the invention provides the reforming catalyst for the production of synthesis gas, it is by comprising following method preparation:
1) by wet method or dry ball milling preparation lanthanum and cerium modified zirconia/alumina support; And
2) blend step 1) in the support powder of preparation and nickel by powder calcining mixt.
According to of the present invention one preferred embodiment, reforming catalyst (NiO-La/Ce-ZrO 2/ Al 2o 3) comprise by weight 1% to 7% with the lanthanum in lanthanum and cerium modified zirconia/alumina support.
According to of the present invention one preferred embodiment, in step 2) in, the temperature of calcining at 700 to 1200 DEG C is carried out in atmosphere.
According to of the present invention one preferred embodiment, in step 2) in, by a series of dry ball milling or wet-mixing, drying, mediate and extrude mixing two kinds of powder.
According to of the present invention one preferred embodiment, reforming catalyst (NiO-La/Ce-ZrO 2/ Al 2o 3) comprise 5% to 20% load by weight with the nickel on lanthanum and cerium modified zirconia/alumina support.If the amount of the nickel of load is outside scope defined above, so may be difficult to produce the synthesis gas of the hydrogen/carbon monoxide ratio with approximate 2.
According to of the present invention one preferred embodiment, reforming catalyst comprises lanthanum and cerium with the weight ratio of 1:2 ~ 10.Outside this scope, may be difficult to produce the synthesis gas of the hydrogen/carbon monoxide ratio with approximate 2.
The present invention is also provided for the method for producing synthesis gas, is included in the temperature of 700 to 950 DEG C, 10 to 20 pressure clung to and 300 to 4000h -1air speed under supply carbon dioxide, steam and methane, and make gas stand reforming reaction in the presence of a catalyst.Preferably supply carbon dioxide and steam with the amount of every mole of methane 0.4 to 1 mole and 1 to 3 mole respectively.The synthesis gas produced by reforming reaction has the hydrogen/carbon monoxide mole ratios of 2.0 ± 0.2.Therefore, method of the present invention can provide the synthesis gas being effective to manufacture petroleum chemicals (such as, wax, naphtha and diesel oil) in an easy manner.
In more detail the present invention will be described now.
Conventional catalyst for steam-CO 2 reforming reaction has inactivation or the active problem reduced under high-speed.On the contrary, by by the nickel Metal Supported of scheduled volume at the mixture can being produced carbon monoxide and hydrogen with reformation Raney nickel of the present invention prepared by lanthanum and cerium modified zirconia/alumina support by the steam-CO 2 reformation of methane (key component of natural gas) with high yield, so-called synthesis gas.
Reformation Raney nickel of the present invention is used for the steam-CO 2 reformation of methane (key component of natural gas), and preferably by NiO-La/Ce-ZrO 2/ Al 2o 3represent, wherein, by weight the nickel of 5% to 20% as active constituent loading with on lanthanum and cerium modified zirconia/alumina support.If the amount of the nickel of load is less than by weight 5%, so catalyst shows bad activity.Meanwhile, if the amount of the nickel of load exceedes by weight 20%, so catalyst due to coke laydown undesirably inactivation.
In the zirconia/alumina support with lanthanum (La) and cerium (Ce) modification, zirconia and aluminium oxide and lanthanum and cerium hydridization (hybridize), lanthanum and cerium exist with the weight ratio of 1:2 ~ 10.The bad activity of catalyst is caused with lanthanum and cerium excess modification carrier.
By Ni on carrier and by a series of dry method or wet-mixing, drying, mediate, extrude and calcining lanthanum and cerium modified zirconia/alumina support.Preferably distilled water is used as solvent.
Most preferably, by mixing the lanthana (La of desired proportion 2o 3), ceria, zirconia, nickel oxide and aluminium oxide obtain with lanthanum and cerium modified zirconia/alumina support.
Nickel oxide is in powder form mixed with lanthanum and cerium modified zirconia/alumina support, mediates, extrude and calcine.Calcining is preferably carried out 5 to 8 hours in atmosphere the temperature of 700 to 1200 DEG C.
The reforming activity of catalyst is measured in the fixed bed catalytic reactor system that typical laboratory manufactures.Before reactions can pretreatment catalyst.Particularly, the also crushing catalyst that is shaped, to have the particle diameter of 1 to 2mm, by the packed catalyst of required amount in the reactor, and passes through 5% hydrogen reducing catalyst 1 hour at 700 DEG C before reactions.
Then, using methane, steam and carbon dioxide as reaction-ure feeding to reactor.Be 1:1 ~ 3 with the mol ratio of methane and steam and the amount that the mol ratio of methane and carbon dioxide is 1:0.4 ~ 1 uses reactant.If needed, add nitrogen as diluent gas.Use electric heater and programmable self-acting thermos that the temperature of reactor is controlled the scope to 700 to 950 DEG C, reaction pressure is adjusted to 10 to 20atm, and service property (quality) flow controller (Mass Flow Controller) controls gas flow rate makes air speed be 3000 to 4000hr -1.The gas of coutroi velocity successive reaction can produce synthesis gas.Use the gas composition before and after gas chromatographicanalyzer analytical reactions, this gas chromatographicanalyzer is connected directly to reactor assembly and is equipped with the Poropak post for gas separaion.
The high temperature active of reforming catalyst is measured at 750 DEG C.By measuring the heat endurance that catalyst is passed in time at the initial activity of 750 DEG C and the conversion ratio assessment reforming catalyst of the activity produced after hydrogen in product 200 minutes and methane.
Reforming catalyst of the present invention for being produced synthesis gas by natural gas shows better more active than the conventional reformation Raney nickel of load on zirconia.Due to the activity of its improvement, catalyst of the present invention even can keep good activity under high gas space velocity, and this shows its potential applicability as industrial catalyst.
Invention pattern
Explain the present invention in more detail with reference to following examples, but be not limited thereto.
preparation embodiment 1
With the aluminium oxide of the ratio mixed-powder form shown in table 1, ceria, zirconia, nickel oxide and lanthana.Distilled water is added into mixture, is fully uniformly mixed, and dry.After abundant mixing, with the speed of 3 DEG C/min, the mixture obtained is heated to 700 ~ 950 DEG C, calcines 6h subsequently to obtain catalyst.
preparation embodiment 2
The ceria of dry powdered form and zirconia are added into aluminium oxide and are mixed by ball milling.With with identical above mode mixed oxidization nickel, lanthana and aluminium oxide.Two kinds of powder are mixed, and at 700 ~ 950 DEG C of calcining 6h to obtain NiO-La/Ce-ZrO 2/ Al 2o 3.
Table 1
[table 1]
Raw material Preparation embodiment 1 (wt%) Preparation embodiment 2 (wt%)
La 2O 3 1～8 1～13
CeO 2 1～13 1～10
NiO 3～12 5～14
ZrO 2 2～10 2～11
Al 2O 3 70～90 70～90
Table 2
[table 2]
embodiment 1-5
By the 7g catalyst application of preparation in preparation embodiment 1 to steam CO 2 reformation SCR (Steam Carbon dioxide Reforming), steam CO 2 reformation carries out and keeps the temperature of 700 ~ 950 DEG C and the pressure of 18 bar.Steam, carbon dioxide and methane is introduced with the ratio shown in table 3.With 3000 ~ 4000hr -1air speed carry out the reformation of methane.Reaction result is shown in table 3 and Fig. 1 and 2.
Table 3
[table 3]
Embodiment number Methane: carbon dioxide: steam CH 4Conversion ratio (%) H 2/CO
Embodiment 1 1:1:1～3 95.93 2.32
Embodiment 2 1:1:1～2.5 94.69 2.11
Embodiment 3 1:1:1～2 93.41 1.92
Embodiment 4 1:0.5～1:1～2 93.31 2.08
Embodiment 5 1:0.4～1:1～2 93.70 2.05
Result as can be seen from table 3, when gas ratio is in the scope of 1:0.4 ~ 1:1 ~ 3, methane conversion remains on 90% or higher and produces the H with 1.9 ~ 2.4 2the synthesis gas of/CO ratio.
embodiment 6-10
Use under the same terms described with embodiment 1 and prepare the catalyst prepared in embodiment 2 and carry out reforming reaction.Result is shown in Table 4.
Table 4
[table 4]
Embodiment number Methane: carbon dioxide: steam CH 4Conversion ratio (%) H 2/CO
Embodiment 6 1:1:1～3 97.07 2.11
Embodiment 7 1:1:1～2.5 95.66 1.95
Embodiment 8 1:1:1～2 95.50 1.91
Embodiment 9 1:0.5～1:1～2 95.32 1.96
Embodiment 10 1:0.4～1:1～2 95.57 2.02
Even when using the catalyst of preparation embodiment 2, obtain similar result.Particularly, when gas ratio is in the scope of 1:0.4 ~ 1:1 ~ 3, methane conversion remains on>=and 95% and produce the H with 1.9 ~ 2.2 2the synthesis gas of/CO ratio.
comparative example 1
Use catalyst disclosed in Korean Patent Application No. 2008-0075787 under the pressure of the temperature of 700 ~ 950 DEG C and 18 bar, carry out the reforming reaction of mixture, Ni is prepared on support C e-Zr/MgAlOx as active constituent loading by use dipping process by this catalyst.Result is shown in Table 5.
Table 5
[table 5]
Reaction mol ratio (CH 4/STM/CO 2) Air speed (hr -1) CH 4Conversion ratio
1/1.5/0.4 1300 95
1/1.5/0.39 1700 93
1/1.5/0.34 1700 97
As can be seen from the above results, at a high space velocity, invention catalyst illustrates and the methane conversion comparing catalyst phase same level.This shows to use invention catalyst can minimize the size of reactor.Particularly, when use invention catalyst time, have the design capacity corresponding to commercial reactors 1/3 ~ 1/5 capacity reactor in can obtain identical CH 4conversion ratio, this confirms the high business efficiency of invention catalyst.
In addition, compared with comparing catalyst with use, when using invention catalyst, CO in reacting gas 2content increase twice or more.From the view point of economy, use a large amount of CO 2be favourable as reacting gas, and reclaim a large amount of remaining CO after reacting 2confirm that SCR process better processes CO than other processes 2ability.
Industrial usability
Catalyst of the present invention minimizes to be produced Carbon deposition in synthesis gas process by the steam-CO 2 reformation (SCR) of methane and can be produced has H 2the synthesis gas of/CO ratio (2.0 ± 0.2), it is effective in the manufacture of petroleum chemicals (such as, wax, naphtha and diesel oil).Therefore, this catalyst is used to contribute to reducing the production cost of synthesis gas and the manufacturing cost of petroleum chemicals.And the method for this catalyst can be used to be applied to GTL (gas-liquid by catalyst of the present invention, gas to liquid) FPSO (floating production, storage and offloading, Floating Production, storage and emptying) system and DME FPSO system.Therefore, expect to find the application of the present invention in multiple industrial circle.

Claims (10)

1. for the production of a reforming catalyst for synthesis gas, by comprising following method preparation:
1) by wet-mixing or dry ball milling preparation lanthanum and cerium modified zirconia/alumina support; And
2) blend step 1) in the support powder of preparation and nickel by powder calcining mixt.
2. reforming catalyst according to claim 1, wherein, reformation is steam-CO 2 reformation.
3. reforming catalyst according to claim 1, wherein, described reforming catalyst comprises described lanthanum and cerium modified zirconia/alumina support (La, the Ce-ZrO of by weight 1% ~ 7% 2/ Al 2o 3) in lanthanum.
4. reforming catalyst according to claim 1, wherein, in step 2) in, described calcining is carried out the temperature of 700 DEG C ~ 1200 DEG C in atmosphere.
5. reforming catalyst according to claim 1, wherein, in step 2) in, described mixing comprises dry ball milling or wet-mixing, drying, kneading and extrudes.
6. reforming catalyst according to claim 1, wherein, described reforming catalyst comprises the load of by weight 5% ~ 20% at described lanthanum and cerium modified zirconia/alumina support (La, Ce-ZrO 2/ Al 2o 3) on nickel.
7. reforming catalyst according to claim 1, wherein, described reforming catalyst comprises lanthanum and cerium with the weight ratio of 1:2 ~ 10.
8., for the production of a method for synthesis gas, be included in the 700 DEG C ~ temperature of 950 DEG C, the pressure of 10atm ~ 20atm and 300h -1~ 4000h -1air speed under supply carbon dioxide, steam and methane, and make these gases stand reforming reaction under reforming catalyst according to any one of claim 1 to 7 exists.
9. method according to claim 8, wherein, supplies carbon dioxide and steam with the amount of every mole of methane 0.4 ~ 1 mole and 1 ~ 3 mole respectively.
10. method according to claim 8, wherein, the synthesis gas produced by described reforming reaction has the hydrogen/carbon monoxide ratio of 2.0 ± 0.2.
CN201380071806.3A 2012-12-12 2013-12-12 Catalyst containing lanthanum for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same Pending CN104955564A (en)

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