CN101462058B - Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry - Google Patents
Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides an industrial catalyst for producing synthesis gas by natural gas-carbon dioxide reforming. The catalyst comprises the following components in percentage by weight: 5 to 19 percent of Ni, 20 to 70 percent of La, and 0 to 2 percent of precious metal; and the catalyst is prepared by powder molding or the impregnation of a carrier by an active constituent, and the carrier is a molecular sieve and a molding additive. The catalyst has high catalytic activity through a micro-reactor and pilot magnification activity evaluation; and compared with other catalysts, the catalyst has strong carbon deposition resistance and steady performance. The catalyst is suitable to produce the synthesis gas by reforming natural gas and carbon dioxide, and also is suitable to produce the synthesis gas by reforming combined raw materials such as flue gas, coke-oven gas and coal bed gas of fuel electric plants, dry gas of oil refineries and the like.
Description
Technical field:
The invention belongs to chemical field, be specifically related to a kind of industrial catalyst of reforming natural gas and carbon dioxide preparing synthetic gas.
Background technology:
Along with the gradually increase to energy demand, the comprehensive utilization of natural gas and minimizing " greenhouse effects " gas discharging has caused people's extensive concern.Natural Gas Resources in China is abundant, but still has the associated gas of oil exploitation and coal seam mine gas not to take full advantage of.And find that there is a large amount of natural gas resource (methane hydrate) in the seabed.In addition, a large amount of CO
2Gas has consisted of global warming, consists of serious threat for the following ecological balance.The main component of natural gas is methane (accounting for 75～95%), and industrialization has been for many years for methane vapor reforming preparing synthetic gas or hydrogen manufacturing.Methane portion oxidation synthesis gas (CH
4+ 1/2O
2=CO+2H
2Δ H=-35.6KJ/mol) method although energy consumption is relatively low, exists catalyst hot issue and potential danger.In addition, if take air as oxidant, need to increase synthesis gas and N
2The separation investment of gas.If take pure oxygen as oxidant, need to increase oxygen from the investment of air separation, therefore fail industrialization always.
Chinese patent 200410065196.9 discloses a kind of with CO
2CH for oxygen source
4The method of portion oxidation synthesis gas.Be CO
2800～1000 ℃ of lower decomposition, and make and decompose the oxygen permeation membrane that the oxygen that produces constantly sees through Ca-Ti ore type, then see through side and methyl hydride catalyzed reaction preparing synthetic gas at film.The method is with directly to separate the method for air oxygen by oxygen permeation membrane similar, and brought CO
2The energy consumption problem that decomposes, and the stability of perovskite oxygen permeation membrane and elevated-temperature seal problem are industrial is difficult to solution.
Natural gas or methane-CO 2 reformation (CH
4+ CO
2=CO+2H
2, Δ H=247kJ/mol) and the preparing synthetic gas reaction is feasible from thermodynamics.And can produce the purity height, CO/H
2Ratio is about 1 synthesis gas.More applicable synthetic by F-T, prepare the diesel raw material of high-quality jet raw material and high cetane number.But owing at the catalyst surface carbon distribution, not only reduced catalyst activity, and the structure of destructible catalyst, even stop up reactor, and energy consumption is relatively high.Therefore, the industrial catalyst of development high activity, high stability is one of key factor that realizes the reforming natural gas and carbon dioxide preparing synthetic gas.
European patent EP 0692451 (1996) discloses at Ni/La
2O
3The method of reforming natural gas and carbon dioxide preparing synthetic gas on the catalyst.At 10mg Ni/La
2O
3With 20mg Al
2O
3On, obtain metastable CH at 750 ℃
4And CO
2Conversion ratio.Think La
2O
3Introducing be conducive to improve the stability of catalyst.But because the Ni direct impregnation is at La
2O
3On the carrier, very low (the about 4m of specific surface area of catalyst
2/ g), experimental result is found, still has a large amount of carbon distributions to produce.
Chinese patent 99110100.6 discloses a kind of preparation method of reforming natural gas and carbon dioxide catalyst for preparing synthetic gas.It is characterized in that cobalt and noble metal (such as Pt, Pd) double activated component loads on γ-Al by infusion process
2O
3On the carrier, this catalyst moves under the low-speed condition, and unstripped gas consists of CH
4/ CO
2=0.69.
Chinese patent 01135912.9 discloses a kind of reforming natural gas and carbon dioxide catalyst for preparing synthetic gas method, and (wherein a kind of is 6～13%Ni, and another kind is 1.5～3.5%MoO to utilize bimetallic
3Or WO
3) active component loads on SiO by infusion process
2And γ-Al
2O
3On the carrier.Although the activity rating result (reaction condition: air speed 8400mL/g.h, 780 ℃ of temperature, normal pressure) in these catalyst 20 hours shows CH
4And CO
2Conversion ratio all more than 90%.But this catalyst is 30～60 purpose beaded catalysts, can not use at industrial large-sized device.Up to the present, the relevant report of estimating is amplified in the preparation and the pilot scale that still have no natural gas/CO 2 reformation industrial catalyst.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides industrial catalyst of a kind of reforming natural gas and carbon dioxide preparing synthetic gas and preparation method thereof and the application in industry is amplified, and is serious to overcome existing catalyst carbon deposit, can't industrialized shortcoming.
Technical scheme
One of technical scheme provided by the invention is a kind of industrial catalyst of reforming natural gas and carbon dioxide preparing synthetic gas, the presoma of the active component of described catalyst is La: the Ni mol ratio is 2 rock-steady structure compound, wherein each composition weight percentage composition is: Ni 5～19%, La 20～70%, noble metal 0～2%, and described catalyst is to form by the powder moulding or by the activity component impregnation carrier.
One of preferred version of above-mentioned catalyst is, described noble metal is one or more among Ru, Rh, the Pd, and the weight percentage in described catalyst is 0.01～2%.
Two of the preferred version of above-mentioned catalyst is that described carrier is ZSM-5, MCM-41, SBA-15 or γ-Al
2O
3In one or more.
As described herein, ZSM-5, MCM-41, SBA-15, γ-Al
2O
3Refer to that respectively (as: ZSM-5 is that specific area is about 250-280m to business-like and synthetic catalyst carrier
2/ g and aperture are the 0.5nm micro porous molecular sieve, γ-Al
2O
3That specific area is about 180-300m
2/ g and aperture are the 3-4nm oxide carrier, and MCM-41 is that specific area is about 600-1100m
2/ g and aperture are 3-4nm mesopore molecular sieve carrier, and SBA-15 is that specific area is about 600-920m
2/ g and aperture are 4-9nm mesopore molecular sieve carrier).
Three of the preferred version of above-mentioned catalyst is that described catalyst is support type or non-loading type.
Four of the preferred version of above-mentioned catalyst is that described catalyst shape is the cylinder of diameter 3mm.
Two of technical scheme provided by the invention is the preparation method of above-mentioned catalyst, in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) the gained gel worn out successively, foam, drying, make each composition weight percentage composition and be: Ni 5～19%, and La 20～70%, the precursor compound of noble metal 0～2%, roasting obtains the powder catalyst;
C) in the powder catalyst, add adhesive, make mechanical-moulded catalyst.
One of preferred version of the preparation method of above-mentioned catalyst is that described noble metal is one or more among Ru, Rh, the Pd.
Two of the preparation method's of above-mentioned catalyst preferred version is, described nickel salt is nickel nitrate or nickelous carbonate, and described lanthanum salt is lanthanum nitrate or lanthana, and described precious metal salt is one or more in chloride, oxide or the nitrate.
Three of the preparation method's of above-mentioned catalyst preferred version is that described organic complexing agent is citric acid or ethylene glycol or its combination; Adhesive is aluminium glue or silica gel or its combination.
Four of the preferred version of above-mentioned method for preparing catalyst is described step b) ageing time be 2～5 days, the baking temperature scope is 70～120 ℃, in constant pressure and dry 10～20 hours, the sintering temperature scope was 500～800 ℃, roasting 6～10 hours.
Three of technical scheme provided by the invention is the preparation method of above-mentioned catalyst, in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) drainage of gained gelinite is entered in the carrier to flood, then dry, roasting obtains catalyst; Wherein, carrier is ZSM-5, MCM-41, SBA-15, γ-Al
2O
3In one or more.
One of preferred version of above-mentioned method for preparing catalyst is described step b) the baking temperature scope be 70～120 ℃, constant pressure and dry 10～20 hours, the sintering temperature scope is 500～800 ℃, roasting 6～10 hours.
Four of technical scheme provided by the invention is a kind of above-mentioned application of catalyst in the industry of reforming natural gas and carbon dioxide preparing synthetic gas is amplified, reaction raw materials is that percent by volume is 0.6～1.0 natural gas and carbon dioxide, range of reaction temperature is 600～950 ℃, reaction pressure scope 0.1～0.8MPa.
Beneficial effect
Catalyst of the present invention amplifies activity rating through microreactor and industry test, and catalytic activity is high, and compares with other catalyst, and anti-carbon can be strong.The life-span is investigated catalyst performance stabilised more than 100 hours.
Industrial catalyst of the present invention is applicable to the industry test amplifying device, not only be adapted to pure natural gas and CO 2 reformation preparing synthetic gas, and be adapted to the combination raw materials preparing synthetic gas by reforming such as flue gas, coke-stove gas, coal bed gas and refinery dry gas in thermal power plant.
The specific embodiment:
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, such as the catalyst handbook, or the condition of advising according to manufacturer.
Embodiment 1
Raw material: nickel nitrate: Ni (NO
3)
2.6H
2O
Lanthanum nitrate: La (NO
3)
3.6H
2O
Citric acid: HO
2CCH
2(OH) (CO
2H) CH
2CO
2H
Ethylene glycol: HOCH
2CH
2OH
Aluminium glue: AlOOH
According to the ratio that La and Ni mol ratio equal 2, prepare certain density Ni (NO
3)
2And La (NO
3)
3Mixed aqueous solution, then add citric acid and the ethylene glycol solution of 1.5 times of concentration of metal ions.Under 50～60 degrees centigrade condition, stirred 20 hours, namely get the gel of green transparent.This gel wore out 2～3 days under constant temperature, and then normal pressure foamed dry 20 hours in 70～80 ℃ of baking ovens.Namely obtain the catalyst based presoma of Ni of porous.The roasting 6 hours in 500 ℃ of air of this presoma can make the Ni-La powder catalyst of nano particle.This catalyst adds 10% aluminium glue and is in harmonious proportion evenly through grinding, and then is processed into
The 3mm industrial catalyst, the Ni weight percentage is that 9～13%, La weight percentage is 34～54% in the component.
In catalyst activity is estimated, industrial catalyst is broken into the beaded catalyst of diameter 1～2mm, in 850 ℃ of hydrogen streams (20mL/min), reduced 1 hour unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1.0, the raw material air speed is 1.01 * 10
4h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.1MPa, 11 hours evaluation result of catalyst sees Table 1.
The activity rating of catalyst among table 1 embodiment 1
Embodiment 2
According to the identical method of embodiment 1, mix La (NO
3)
3And Ni (NO
3)
2Solution adds a small amount of RuCl
3Or RhCl
3In mixed liquor, dissolve, then add the organic reagents such as citric acid of 1.5 times of concentration of metal ions.
Stirring under 60 ℃ the condition more than 10 hours, to form homogeneous transparent Ni-M-La colloidal sol (M=Ru and/or Rh).At room temperature aging 4～5 days, the normal pressure dry 10h that foams in 110～120 ℃ baking oven.Then roasting 6 hours in 800 ℃ Muffle furnace namely makes and contains noble metal Ru or Rh (0.01～2%) nickel base nanometer catalyst.Then prepare according to embodiment 1 same procedure
The cylindrical industrial catalyst of 3mm, each composition weight percentage composition is: Ni 9～15%, and La 17～35%, and Ru 0.4%.In catalyst activity is estimated, the beaded catalyst that catalyst breakage becomes diameter 1～2mm is amplified in industry.At 850 ℃, reduction is 1 hour among the hydrogen flow rate 20mL/min, unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1: 1.The raw material air speed is 3.35 * 10
3h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.11MPa, 103 hours activity ratings of catalyst the results are shown in Table 2.
The activity rating of catalyst among table 2 embodiment 2
Embodiment 3
According to the identical method of embodiment 1, with La (NO
3)
3And Ni (NO
3)
2Mixed liquor inject the commercially available ZSM-5 molecular sieve of 200g (available from Catalyst Factory, Nankai Univ), constantly flooding 5 hours under the stirring condition, then add 1.5 times of concentration of metal ions citric acids and ethylene glycol, stir 60 ℃ conditions and make the gelinite that contains the ZSM-5 carrier.The method of then pressing embodiment 1 is aging, foaming and dry in baking oven, and at last 550 ℃ of roastings 6 hours in Muffle furnace namely obtain the supported catalyst of nickeliferous 9% (weight ratio).Then according to the method for executing example 1 prepare the 9%Ni-La/ZSM-5 industrial catalyst (
3mm), each composition weight percentage composition is: Ni 9%, and La 40～46%, and all the other are carrier, adhesive and auxiliary agent.
The filling industrial catalyst is 0.3 kilogram in the reactor that industry is amplified.With this catalyst at 850 ℃, 20%H
2/ N
2Reduction is 8 hours in the gaseous mixture, and feeding gas is that (mol ratio is CH for natural gas and carbon dioxide
4/ CO
2=1.0～0.6).Under the differential responses condition, the composition of exit gas sees Table 3.
The activity rating of catalyst among table 3 embodiment 3
Embodiment 4
According to the catalyst activity appreciation condition of embodiment 3, changing charging CH
4/ CO
2Ratio after, it the results are shown in Table 4.
The activity rating of catalyst under different feeds ratio of components condition among table 4 embodiment 4
Embodiment 5
In catalyst activity is estimated, the industrial catalyst among the embodiment 3 is broken into the beaded catalyst of diameter 1～2mm.Be reduction 1 hour under the condition of 20mL/min at 850 ℃, hydrogen flow rate before the reaction, CH in the unstripped gas
4/ CO
2Ratio of components be 0.98.The raw material air speed is 6.3 * 10
3h
-1, reaction temperature is that 850 ℃, reaction pressure are 0.1MPa, 80 hours evaluation results of catalyst see Table 5.
The activity rating of catalyst among table 5 embodiment 5
Embodiment 6
Preparing the Ni weight percentage according to embodiment 3 identical methods is 10% Ni/La
2O
3/ MCM-41 catalyst, surplus composition are that mass ratio is 45: 55 carrier La
2O
3And MCM-41 (department of chemistry of University Of Tianjin catalyst chamber is synthetic according to open source literature J.Catal.249 (2007) 102).
In catalyst and activity rating, at 700 ℃, hydrogen flow rate is to reduce 1 hour unstripped gas (CH under the 20mL/min condition before the reaction
4/ CO
2) ratio of components be 1: 1.The raw material air speed is 1.17 * 10
4h
-1, reaction temperature is that 850 ℃, reaction pressure are 0.1MPa, 10 hours evaluation results of catalyst see Table 6.
The activity rating of catalyst among table 6 embodiment 6
Embodiment 7
With reference to embodiment 1 same procedure, the preparation La: the Ni mol ratio is 2 presoma, then by dipping method with commercially available ZSM-5 carrier (
3mm is available from Catalyst Factory, Nankai Univ) mix with rare colloidal sol of nickel active component.Under continuous stirring condition with the rare sol impregnation ZSM-5 molecular sieve of this presoma 36 hours.Under 120 ℃ of conditions after the drying, 550 ℃ of calcined catalyst samples are 6 hours in Muffle furnace.What namely obtain support type contains the industrial catalyst that the Ni weight percentage is 6～9% Ni/La/ZSM-5, wherein La
2O
3Weight percentage is lower than 20%.
With reference to embodiment 2 the same terms, directly applicable industry is carried out activity rating with cylinder shape catalyst, and at 850 ℃, hydrogen flow rate is 20mL/min reduction 1 hour, unstripped gas (CH before the reaction
4/ CO
2) ratio of components be 1: 1.The raw material air speed is 1.2 * 10
3h
-1, 850 ℃ of reaction temperatures, reaction pressure 0.1MPa, 100 hours activity ratings of catalyst the results are shown in Table 7.
The activity rating of catalyst among table 7 embodiment 7
Claims (10)
1. the industrial catalyst of a reforming natural gas and carbon dioxide preparing synthetic gas, described catalyst components weight percentage is: Ni 5～19%, and La 20～70%, noble metal 0～2%, and described catalyst is to form by the powder moulding;
Wherein, the preparation method of powder moulding in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) the gained gel worn out successively, foam, drying, make each composition weight percentage composition and be: Ni 9～15%, and La 17～54%, the precursor compound of noble metal 0～2%, roasting obtains the powder catalyst;
C) in the powder catalyst, add adhesive, make mechanical-moulded catalyst.
2. catalyst according to claim 1 is characterized in that, described noble metal is one or more among Ru, Rh, the Pd, and the content in described catalyst is 0.01～2%wt.
3. catalyst according to claim 1 is characterized in that, described catalyst shape is the cylinder of diameter 3mm.
4. the preparation method of a catalyst claimed in claim 1 in turn includes the following steps:
A) with nickel salt, lanthanum salt, precious metal salt dissolving, add organic complexing agent, stir and form the sol-gel body;
B) the gained gel worn out successively, foam, drying, make each composition weight percentage composition and be: Ni 5～19%, and La 20～70%, the precursor compound of noble metal 0～2%, roasting obtains the powder catalyst;
C) in the powder catalyst, add adhesive, make mechanical-moulded catalyst.
5. the preparation method of catalyst according to claim 4 is characterized in that, described noble metal is one or more among Ru, Rh, the Pd.
6. the preparation method of catalyst according to claim 4 is characterized in that, described nickel salt is nickel nitrate or nickelous carbonate, and described lanthanum salt is lanthanum nitrate, and described precious metal salt is one or more in chloride or the nitrate.
7. the preparation method of catalyst according to claim 6 is characterized in that, described lanthanum salt substitutes with lanthana.
8. the preparation method of catalyst according to claim 6 is characterized in that, described precious metal salt substitutes with metal oxide containing precious metals.
9. the preparation method of catalyst according to claim 6 is characterized in that, described organic complexing agent is citric acid or ethylene glycol or its combination; Adhesive is aluminium glue or silica gel or its combination.
10. the application of catalyst claimed in claim 1 in the industry of reforming natural gas and carbon dioxide preparing synthetic gas is amplified, reaction raw materials is that percent by volume is 0.6～1.0 natural gas and carbon dioxide, range of reaction temperature is 600～950 ℃, reaction pressure scope 0.1～0.8MPa.
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|---|---|---|---|
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110207972A1 (en) * | 2010-02-23 | 2011-08-25 | Battelle Memorial Institute | Catalysts and processes for the hydrogenolysis of glycerol and other organic compounds for producing polyols and propylene glycol |
| CN102745648A (en) * | 2011-04-22 | 2012-10-24 | 太原理工大学 | Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation |
| CN103041839A (en) * | 2012-12-04 | 2013-04-17 | 华南理工大学 | Nickel-based bi-metallic catalyst with SBA-15 serving as a carrier and preparation method and application of catalyst |
| CN103599785A (en) * | 2013-11-27 | 2014-02-26 | 上海大学 | Spinel-supported catalyst for dry reforming of coke oven gas and preparation method thereof |
| CN106520179A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas |
| CN106520178A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and small-size coke prepared gas |
| CN106520177A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method of directly preparing fuel oil from coke oven gas |
| CN106345480B (en) * | 2016-08-01 | 2018-10-19 | 陕西省能源化工研究院 | A kind of catalyst series for hydro carbons CO 2 reforming reaction and its preparation method and application method |
| CN106311251A (en) * | 2016-08-30 | 2017-01-11 | 上海大学 | Preparation method of mesoporous silica supported high-dispersion nickel-lanthanum oxide catalyst |
| CN108295905A (en) * | 2018-02-06 | 2018-07-20 | 重庆理工大学 | A kind of surfactant enhancing CO2The preparation method and application of reforming catalyst |
| CN110732346A (en) * | 2018-07-18 | 2020-01-31 | 华东理工大学 | polymetallic methanation catalyst, and preparation method and application thereof |
| CN109590011A (en) * | 2019-01-23 | 2019-04-09 | 华东师范大学 | A kind of Ni base catalyst and preparation method thereof and the application in synthesis gas is being prepared using coal oil tail gas as raw material |
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| CN1234366A (en) * | 1999-05-14 | 1999-11-10 | 清华大学 | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof |
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2007
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|---|---|---|---|---|
| CN1234366A (en) * | 1999-05-14 | 1999-11-10 | 清华大学 | Nickel-base catalyst for preparing synthetic gas by reforming methane with carbon dioxide and preparation method thereof |
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| Title |
|---|
| Zhenxing Cheng et al..Effects of promoters and preparation procedures on reforming of methane with carbon dioxide over Ni/Al2O3 catalyst.《Catalysis Today》.1996,第30卷147-155. * |
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Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
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Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Patentee after: Tianjin University Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. Patentee before: Tianjin University |