CN108499568A - A kind of nickel-base catalyst of carbon dioxide pressurized reforming methane - Google Patents

A kind of nickel-base catalyst of carbon dioxide pressurized reforming methane Download PDF

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CN108499568A
CN108499568A CN201810410946.3A CN201810410946A CN108499568A CN 108499568 A CN108499568 A CN 108499568A CN 201810410946 A CN201810410946 A CN 201810410946A CN 108499568 A CN108499568 A CN 108499568A
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catalyst
nickel
auxiliary agent
carbon dioxide
nitrate
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CN108499568B (en
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刘忠文
肖勇山
李婷
石先莹
宋永红
刘昭铁
杨策敬
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Shaanxi Normal University
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Abstract

The invention discloses a kind of nickel-base catalysts of carbon dioxide pressurized reforming methane, and the carrier of the catalyst is SiO2、Al2O3、TiO2At least one of, active constituent Ni, Ni Fe or Ni Co, auxiliary agent CeO2、ZrO2Or CexZr1‑xO2, the wherein value of x is 0.3~0.7；It is in terms of 100% by the quality of catalyst, the content of active component is 5%~15%, and the content of auxiliary agent is 2%~9%, remaining is carrier；The catalyst be with glycine, alanine, threonine, citric acid, oxalic acid etc. be complexant and combustion adjuvant, using coordination decomposition method be prepared, preparation process is simple, and cost is relatively low, economic and environment-friendly.Catalyst of the present invention has higher methane and carbon dioxide conversion ratio to reforming methane with carbon dioxide under an increased pressure, shows high activity, high stability and high anti-carbon and anti-caking power.

Description

A kind of nickel-base catalyst of carbon dioxide pressurized reforming methane
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of for pressurized conditions carbon dioxide reforming methane Catalyst.
Background technology
In recent years, with the intensification that people recognize greenhouse effects, the CO as most one of strong greenhouse gas2Capture and Its application causes increasingly extensive attention.Reforming methane with carbon dioxide can utilize CO simultaneously2And CH4Two big greenhouse gases, to temperature Room gas abatement is of great significance, and the H of synthesis gas2/ CO≤1 can be used as the original of carbonyl and organic oxygen-containing compound synthesis Expect gas.From Ashcroft etc. (Nat.Chem., 1991,352:After 225-226) reporting reforming methane with carbon dioxide research, two Carbonoxide reforming methane causes the extensive concern of various countries worker.
The catalyst system of reforming methane with carbon dioxide is broadly divided into two classes, and one kind is noble metal (Pt, Rh, Ru, Pd, Ir) For the catalyst of active component, such catalyst is although have high activity, selectivity and stability, limited source, price It is expensive, it is difficult to realize commercial applications.Another kind of is the catalyst that group VIII base metal (Fe, Ni, Co) is active component, Active sequence is Ni>Co>Fe, wherein Ni bases catalyst are with high catalytic activity and cheap and easy to get receive significant attention.However, Ni Also there is easy carbon distribution and sintering disadvantage and catalytic activity caused to decline in base catalyst.Therefore, reforming methane with carbon dioxide at present Hot spot is mainly concentrated in the stability and anti-carbon performance for improving Ni base catalyst.Theoretical research shows smaller Ni particles Size could inhibit nucleation and the growth of fibrous carbon, to achieve the purpose that anti-carbon.In practical applications, Ni bases catalyst is logical It is prepared frequently with infusion process, the precipitation method or sol-gel method, catalyst prepared by these methods can be kept in a short time Preferable catalytic activity and stability, but in the operation of long period methane reforming reaction by using carbon dioxide, active component is easily reunited Sintering and carbon distribution and cause to inactivate.
Reforming methane with carbon dioxide need to react at high temperature, thus the carrier selected by nickel-base catalyst must have it is good Thermal stability, such as Al2O3、SiO2、MgO、MgO-Al2O3、CeO2-ZrO2And mesopore molecular sieve, foamed ceramics etc..There is document report Road (Applied Catalysis A:General, 2016,520,140-150), Ce0.5Zr0.5-SiO2Supported ni catalyst is used In methane reforming reaction by using carbon dioxide, although sol-gel method prepares Ce0.5Zr0.5-SiO2The mesopore orbit of carrier is to nickel particle There is certain confinement effect, but because its specific surface area is smaller, in atmospheric conditions after 700 DEG C of reactions 45 hours, catalyst is apparent Inactivation.In addition, the nickel-base catalyst overwhelming majority of existing exploitation is using normal pressure methane reforming reaction by using carbon dioxide as probe reaction, And the storage and transport of natural gas are condition of high voltage, and using synthesis gas as source transformation technology (such as Fischer-Tropsch synthesis With synthesizing methanol etc.) it is also to realize at elevated pressures, therefore in terms of total energy efficiency angle, the methane under pressurized conditions Reforming process is more reasonable, efficient.It is analyzed from aerodynamic point, raising reaction rate is more advantageous under pressurized conditions, and be catalyzed The rate that the carbon deposition rate and carbon on agent surface are eliminated can also be accelerated.When the carbon deposition rate of catalyst surface is more than the speed that carbon distribution is eliminated When rate, catalyst will accelerate carbon distribution to inactivate, or even blocking bed causes termination to be reacted.
Research group (Ind.Eng.Chem.Res.2014,53,19077-19086 where inventor；Int.J.of Hydrogen Energy.2014,39,11592-11605) using carboxylic acid or amino acid as complexing agent, it is prepared using decomposition by combustion Ni/SiO2Catalyst is used for carbon dioxide pressurized methane reforming reaction, when reaction pressure is improved from 1.0atm to 10atm, instead After answering 20h, the carbon deposition quantity of catalyst increases to 80wt% from 2.0wt%, although the catalyst has certain appearance carbon ability, As area carbon gradually increases, once carbon deposition quantity has been more than the appearance carbon ability of catalyst, for catalyst by rapid deactivation, carbon distribution is stifled Plug bed terminates reaction to have to.
From the foregoing, it can be seen that the catalyst for the methane reforming reaction by using carbon dioxide energy stable operation developed under existing normal pressure is adding Carbon distribution is particularly acute under the conditions of pressure, and catalyst bed is made to be blocked because of carbon distribution, causes methane reforming reaction by using carbon dioxide can not be after It is continuous.Therefore, the catalyst for methane reforming reaction by using carbon dioxide obtained under an increased pressure with high activity and anti-carbon is current The emphasis of research.
Invention content
Technical problem to be solved by the present invention lies in overcoming under above-mentioned pressurized conditions, reforming methane with carbon dioxide catalyst Easy carbon distribution and the shortcomings that lead to inactivation, a kind of CO 2 reformation high, stability is good active under an increased pressure is provided Methane nickel-base catalyst.
The carrier for solving catalyst used by above-mentioned technical problem is SiO2、Al2O3、TiO2At least one of, activity at It is divided into Ni, Ni-Fe or Ni-Co, auxiliary agent CeO2、ZrO2Or CexZr1-xO2, the wherein value of x is 0.3~0.7；With catalyst Quality be 100% meter, the content of active component is 5%~15%, and the content of auxiliary agent is 2%~8%, remaining is carrier；It should Catalyst is prepared by the following method：
According to the composition of catalyst, active component presoma, auxiliary agent presoma, support precursor are dissolved in ethyl alcohol, so The aqueous solution of coordination-combustion adjuvant is added afterwards, is stirred at room temperature 2~4 hours, solvent is evaporated off, obtains viscous liquid, which is added Heat burning roasts 3~6 hours after the solid powder grinding uniformly burnt in 500~750 DEG C of air atmosphere, natural It is cooled to room temperature, tabletting, is granulated, cross 40~60 mesh sieve, obtain catalyst.
Above-mentioned coordination-combustion adjuvant be glycine, alanine, threonine, serine, ethylenediamine, citric acid, urea, Any one in any one in benzenetricarboxylic acid, niacin, oxalic acid, preferably glycine, alanine, threonine；Coordination-combustion adjuvant Addition is metallic element in metallic element in metallic element, auxiliary agent presoma in active component presoma and support precursor Or/and 0.5~2 times of metalloid element integral molar quantity, preferably 1~1.5 times.
It is in terms of 100% by the quality of catalyst, preferably the content of active component is 10%, auxiliary agent in above-mentioned catalyst Content is 4%~7%；Further preferred auxiliary agent is CexZr1-xO2。
When above-mentioned active component is Ni, active component presoma is nickel nitrate or nickel oxalate；When active component is Ni-Fe, Active component presoma is any one in nickel nitrate, nickel oxalate and any one in ferric nitrate, ferric oxalate, ferric citrate Mixture；When active component is Ni-Co, active component presoma is any one in nickel nitrate, nickel oxalate and cobalt nitrate, acetyl The mixture of any one in acetone cobalt, cobalt oxalate.
Above-mentioned auxiliary agent is CeO2When, auxiliary agent presoma is cerous nitrate or ammonium ceric nitrate；Auxiliary agent is ZrO2When, auxiliary agent presoma For zirconium nitrate or zirconyl nitrate；Auxiliary agent is CexZr1-xO2When, auxiliary agent presoma is any one in cerous nitrate, ammonium ceric nitrate and nitre The mixture of any one in sour zirconium, zirconyl nitrate.
Above-mentioned support precursor is methyl silicate, ethyl orthosilicate, silicic acid propyl ester, butyl silicate, aluminium isopropoxide, nitric acid At least one of aluminium, boehmite, butyl titanate, isopropyl titanate.
In the preparation method of above-mentioned catalyst, it is small that 3~6 are roasted further preferably in 650~750 DEG C of air atmosphere When.
Beneficial effects of the present invention are as follows：
1, the present invention uses coordination-decomposition method, in the preparation process of catalyst, coordination-combustion adjuvant energy and active component Metal cation coordination in presoma, auxiliary agent presoma forms complex, can be true during evaporation of the solvent, conflagration The high degree of dispersion of metal cation is protected, the relatively strong interaction of metal and carrier is formed；The CeO that auxiliary agent forerunner's precursor reactant generates2、 ZrO2、CexZr1-xO2With low-temperature reduction and basic site, be conducive to adsorb and activate CO in pyroreaction2, to carry High catalytic activity, while CeO2、ZrO2、CexZr1-xO2Stronger interaction can occur with Ni, keep active metal anti-in high temperature Aggregation not easy to migrate in answering keeps smaller metallic particles.In addition, CeO2、ZrO2、CexZr1-xO2Also there is good storage oxygen energy Power, oxygen mobility energy and high high-temp stability help to activate CO2Eliminate the carbon distribution generated in pressurization methane dry reforming.
2, the specific surface area of nickel-base catalyst of the present invention is 500~650m20.30~0.55cm of/g, Kong Rongwei3/ g, aperture It is distributed as 0.6~1.0nm, for active component particles size in 4.0~9nm or so, particle diameter distribution is relatively narrow, is conducive to inhibit Ni-based to urge The carbon distribution on agent surface generates, and turns under an increased pressure with higher methane and carbon dioxide to reforming methane with carbon dioxide Rate shows high activity, high stability and high anti-carbon and anti-caking power.
Specific implementation mode
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities Apply example.
Embodiment 1
Become 10%Ni-5%CeO according to catalyst group2-SiO2, by six nitric hydrate ceriums of 0.4150g (0.956mmol) and 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.6963g (46.543mmol) ethyl orthosilicate are dissolved in 40g ethyl alcohol, are obtained Solution A.6.6948g (53.104mmol) oxalic acid dihydrate is dissolved in 40g distilled water again, obtains solution B.By solution B plus Enter in solution A, be stirred at room temperature 4 hours, solvent is evaporated off with Rotary Evaporators, obtains viscous liquid, move on electrothermal furnace and burn, The solid powder that burning obtains is placed in Muffle furnace and is roasted, is warming up to 700 DEG C with 5 DEG C/min of heating rate, constant temperature is kept 4 hours, cooled to room temperature was taken out, tabletting, is granulated, and crosses 40~60 mesh sieve, is prepared into catalyst, specific surface area is 575m2/ g, Kong Rong are 0.38cm3/ g, pore-size distribution 0.81nm.
Embodiment 2
Become 10%Ni-5%ZrO according to catalyst group2-SiO2, by two nitric hydrate oxygen of 0.3567g (1.335mmol) Zirconium, 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.6963g (46.543mmol) ethyl orthosilicate are dissolved in 40g ethyl alcohol, Obtain solution A.5.6194g (53.48mmol) Citric Acid Mono is dissolved in 40g distilled water again, obtains solution B.By solution B plus Enter in solution A, be stirred at room temperature 4 hours, solvent is evaporated off with Rotary Evaporators, obtains viscous liquid, move on electrothermal furnace and burn, The solid powder that burning obtains is placed in Muffle furnace and is roasted, is warming up to 700 DEG C with 5 DEG C/min of heating rate, constant temperature is kept 4 hours, cooled to room temperature was taken out, tabletting, is granulated, and crosses 40~60 mesh sieve, is prepared into catalyst, specific surface area is 569m2/ g, Kong Rong are 0.35cm3/ g, pore-size distribution 0.78nm.
Embodiment 3
Become 10%Ni-4.5%Ce according to catalyst group0.5Zr0.5O2-SiO2, 0.1340g (0.501mmol) two is hydrated Zirconyl nitrate, six nitric hydrate ceriums of 0.2177g (0.501mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.7534g (46.817mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.It is again that 6.0158g (53.424mmol) glycine is molten In 40g distilled water, solution B is obtained.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 614m2/ g, Kong Rong are 0.39cm3/ g, pore-size distribution 0.77nm.
Embodiment 4
Become 10%Ni-9%Ce according to catalyst group0.5Zr0.5O2-SiO2, 0.2678g (1.003mmol) two is hydrated nitre Sour oxygen zirconium, six nitric hydrate ceriums of 0.4353g (1.003mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.2400g (44.3534mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.Again by 2.3147g (51.9627mmol) alanine It is dissolved in 40g distilled water, obtains solution B.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 540m2/ g, Kong Rong are 0.37cm3/ g, pore-size distribution 0.80nm.
Embodiment 5
Become 10%Ni-5%Ce according to catalyst group0.7Zr0.3O2-SiO2, 0.0837g (0.313mmol) two is hydrated nitre Sour oxygen zirconium, six nitric hydrate ceriums of 0.3175g (0.731mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.6963g (46.543mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.It is again that 6.3368g (53.190mmol) threonine is molten In 40g distilled water, solution B is obtained.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 581m2/ g, Kong Rong are 0.40cm3/ g, pore-size distribution 0.83nm.
Embodiment 6
Become 10%Ni-5%Ce according to catalyst group0.6Zr0.4O2-SiO2, 0.1152g (0.431mmol) two is hydrated nitre Sour oxygen zirconium, six nitric hydrate ceriums of 0.2809g (0.6471mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrates and 9.6963g (46.543mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.It is again that 3.9955g (53.223mmol) glycine is molten In 40g distilled water, solution B is obtained.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 579m2/ g, Kong Rong are 0.38cm3/ g, pore-size distribution 0.78nm.
Embodiment 7
Become 5%Ni-5%Ce according to catalyst group0.5Zr0.5O2-SiO2, 0.4837g (1.114mmol) six is hydrated nitre Sour cerium, five nitric hydrate zirconiums of 0.4782g (1.114mmol), 1.226g (5.605mmol) nickel oxalates and 20.5333g (98.563mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.Again by 7.9871g (106.396mmol) glycine It is dissolved in 40g distilled water, obtains solution B.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 615m2/ g, Kong Rong are 0.43cm3/ g, pore-size distribution 0.77nm.
Embodiment 8
Become 10%Ni-5%Ce according to catalyst group0.5Zr0.5O2-TiO2-SiO2, by 0.3054g (0.557mmol) nitre Sour cerium ammonium, five nitric hydrate zirconiums of 0.2391g (0.557mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrate, 8.5557g (41.068mmol) ethyl orthosilicate and 1.4018g (4.1200mmol) butyl titanate are dissolved in 40g ethyl alcohol, obtain solution A. 3.8967g (51.907mmol) glycine is dissolved in 40g distilled water again, obtains solution B.Solution B is added in solution A, room Temperature stirring 4 hours, is evaporated off solvent with Rotary Evaporators, obtains viscous liquid, move on electrothermal furnace and burn, and burning is obtained Solid powder is placed in roasting in Muffle furnace, is warming up to 700 DEG C with 5 DEG C/min of heating rate, constant temperature is kept for 4 hours, naturally cold But it to room temperature, takes out, tabletting, is granulated, cross 40~60 mesh sieve, be prepared into catalyst, specific surface area is 561m2/ g, Kong Rong are 0.38cm3/ g, pore-size distribution 0.92nm.
Embodiment 9
Become 10%Ni-5%Ce according to catalyst group0.5Zr0.5O2-Al2O3-SiO2, by 0.3054g (0.557mmol) nitre Sour cerium ammonium, five nitric hydrate zirconiums of 0.2391g (0.557mmol), 1.63g (5.605mmol) Nickelous nitrate hexahydrate, 1.3175g (6.450mmol) aluminium isopropoxide and 8.5562g (41.070mmol) ethyl orthosilicate are dissolved in 40g ethyl alcohol, obtain solution A.Again 4.0717g (54.239mmol) glycine is dissolved in 40g distilled water, solution B is obtained.Solution B is added in solution A, room temperature Stirring 4 hours, is evaporated off solvent with Rotary Evaporators, obtains viscous liquid, move on electrothermal furnace and burn, and consolidates what burning obtained Body powder is placed in roasting in Muffle furnace, is warming up to 700 DEG C with 5 DEG C/min of heating rate, constant temperature is kept for 4 hours, natural cooling It to room temperature, takes out, tabletting, is granulated, cross 40~60 mesh sieve, be prepared into catalyst, specific surface area is 588m2/ g, Kong Rong are 0.45cm3/ g, pore-size distribution 0.91nm.
Embodiment 10
Become 10%Ni-5%Ce according to catalyst group0.5Zr0.5O2-TiO2-Al2O3-SiO2, by 0.3054g (0.557mmol) ammonium ceric nitrate, five nitric hydrate zirconiums of 0.2391g (0.557mmol), six nitric hydrates of 1.63g (5.605mmol) Nickel, 0.7007g (2.0589mmol) butyl titanate, 0.6588g (3.2258mmol) aluminium isopropoxides and 8.5562g (41.070mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.Again by 3.9842g (53.0737mmol) glycine It is dissolved in 40g distilled water, obtains solution B.Solution B is added in solution A, is stirred at room temperature 4 hours, is evaporated off with Rotary Evaporators molten Agent obtains viscous liquid, moves on electrothermal furnace and burns, and the solid powder that burning obtains is placed in Muffle furnace and is roasted, with 5 DEG C/min heating rate be warming up to 700 DEG C, constant temperature is kept for 4 hours, cooled to room temperature, is taken out, tabletting, is granulated, and crosses 40 ~60 mesh sieve, and are prepared into catalyst, specific surface area is 578m2/ g, Kong Rong are 0.44cm3/ g, pore-size distribution 0.88nm.
Embodiment 11
Become 8%Ni-2%Fe-5%Ce according to catalyst group0.5Zr0.5O2-Al2O3-SiO2, by 0.1862g (0.6962mmol) two nitric hydrate oxygen zirconium, six nitric hydrate ceriums of 0.3022g (0.6962mmol), 1.63g (5.605mmol) six Nitric hydrate nickel, 0.5948g (1.4724mmol) Fe(NO3)39H2O, 1.6468g (8.0633mmol) aluminium isopropoxides and 10.6946g (51.335mmol) ethyl orthosilicate is dissolved in 40g ethyl alcohol, obtains solution A.Again by 6.0464g (67.8681mmol) alanine is dissolved in 40g distilled water, obtains solution B.Solution B is added in solution A, it is small to be stirred at room temperature 4 When, solvent is evaporated off with Rotary Evaporators, obtains viscous liquid, moves on electrothermal furnace and burns, the solid powder that burning is obtained It is placed in roasting in Muffle furnace, is warming up to 700 DEG C with 5 DEG C/min of heating rate, constant temperature is kept for 4 hours, naturally cools to room Temperature is taken out, tabletting, is granulated, and crosses 40~60 mesh sieve, is prepared into catalyst, specific surface area is 582m2/ g, Kong Rong are 0.44cm3/ G, pore-size distribution 0.89nm.
Embodiment 12
Become 9%Ni-1%Co-5%Ce according to catalyst group0.5Zr0.5O2-TiO2-SiO2, by 0.1653g (0.6188mmol) two nitric hydrate oxygen zirconium, six nitric hydrate ceriums of 0.2687g (0.6188mmol), 0.1805g (0.6198mmol) cabaltous nitrate hexahydrate, 1.63g (5.605mmol) Nickelous nitrate hexahydrate, 9.5063g (45.6311mmol) are just Silester and 1.5575g (4.5766mmol) butyl titanate are dissolved in 40g ethyl alcohol, obtain solution A.Again by 4.3293g (57.67mmol) glycine is dissolved in 40g distilled water, obtains solution B.Solution B is added in solution A, is stirred at room temperature 4 hours, Solvent is evaporated off with Rotary Evaporators, obtains viscous liquid, moves on electrothermal furnace and burns, the solid powder that burning obtains is placed in Roasting in Muffle furnace is warming up to 700 DEG C with 5 DEG C/min of heating rate, and constant temperature is kept for 4 hours, and cooled to room temperature takes Go out, tabletting, be granulated, crosses 40~60 mesh sieve, be prepared into catalyst, specific surface area is 575m2/ g, Kong Rong are 0.45cm3/ g, hole Diameter is distributed as 0.91nm.
In order to prove that beneficial effects of the present invention, inventor are used for catalyst prepared by embodiment 1~12 to be catalyzed dioxy Change carbon methane reforming reaction, specific test method is as follows：
0.15g catalyst is placed in fixed bed reactors, H is passed through2With N2Volume ratio is 2:8 gaseous mixture, flow are 50mL·min-1, with 4 DEG C of min-1Heating rate rise to 700 DEG C from room temperature, reductase 12 .5 hours.Then, H is closed2, continue It is passed through N2, with 2 DEG C of min-1Heating rate be warming up to 750 DEG C, after temperature stabilization after, be switched to reaction gas (CO2With CH4Body Product is than the gaseous mixture for 1: 1), the total amount of reaction gas is 130mLmin-1, in P=1.0MPa, T=750 DEG C, CO2/CH4= 1.0, air speed=53200mLg-1·h-1Under the conditions of react, the gas after reaction by Shanghai China love GC9560 type conductance cells detect Chromatograph (chromatographic column is 5A and PQ columns) detection and analysis of device, experimental result are shown in Table 1.
Table 1
Embodiment 7
By table 1 as it can be seen that catalyst of the present invention under an increased pressure to reforming methane with carbon dioxide have higher methane and Carbon dioxide conversion, in P=1.0MPa, T=750 DEG C, CO2/CH4=1.0, air speed=53200mLg-1·h-1Under the conditions of, When the content of W metal or Ni-Fe or Ni-Co are 10% in catalyst, methane initial conversion is all up 48% or more, dioxy Change carbon initial conversion up to 68% or more, service life length, the stability of catalyst are high, after successive reaction 100h, activity It is basicly stable constant.

Claims (9)

1. a kind of nickel-base catalyst of carbon dioxide pressurized reforming methane, it is characterised in that：The carrier of the catalyst is SiO2、 Al2O3、TiO2At least one of, active constituent Ni, Ni-Fe or Ni-Co, auxiliary agent CeO2、ZrO2Or CexZr1-xO2, wherein x Value be 0.3~0.7；It is in terms of 100% by the quality of catalyst, the content of active component is 5%~15%, the content of auxiliary agent It is 2%~9%, remaining is carrier；The catalyst is prepared by the following method：
According to the composition of catalyst, active component presoma, auxiliary agent presoma, support precursor are dissolved in ethyl alcohol, then added The aqueous solution for entering coordination-combustion adjuvant is stirred at room temperature 2~4 hours, solvent is evaporated off, obtains viscous liquid, which is heated and is fired It burns, after the solid powder grinding uniformly burnt, is roasted 3~6 hours in 500~800 DEG C of air atmosphere, natural cooling To room temperature, tabletting is granulated, and is crossed 40~60 mesh sieve, is obtained catalyst；
Above-mentioned coordination-combustion adjuvant is glycine, alanine, threonine, serine, ethylenediamine, citric acid, urea, equal benzene three Any one in formic acid, niacin, oxalic acid, the addition of coordination-combustion adjuvant are in active component presoma before metallic element, auxiliary agent Drive in body metallic element in metallic element and support precursor or/and metalloid element integral molar quantity 0.5~2 times.
2. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 1, it is characterised in that：With catalyst Quality be 100% meter, the content of active component is 10%, and the content of auxiliary agent is 4%~7%.
3. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 2, it is characterised in that：The auxiliary agent For CexZr1-xO2。
4. the nickel-base catalyst of the carbon dioxide pressurized reforming methane according to claims 1 to 3 any one, feature exist In：Coordination-the combustion adjuvant is any one in glycine, alanine, threonine.
5. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 4, it is characterised in that：It is described to match The addition of position-combustion adjuvant is metallic element and carrier forerunner in metallic element, auxiliary agent presoma in active component presoma 1~1.5 times of metallic element or/and metalloid element integral molar quantity in body.
6. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 1, it is characterised in that：The activity When group is divided into Ni, active component presoma is nickel nitrate or nickel oxalate；When the active component is Ni-Fe, active component forerunner Body is the mixture of any one and any one in ferric nitrate, ferric oxalate, ferric citrate in nickel nitrate, nickel oxalate；It is described When active component is Ni-Co, active component presoma is nickel nitrate, any one in nickel oxalate and cobalt nitrate, acetylacetone cobalt, The mixture of any one in cobalt oxalate.
7. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 1, it is characterised in that：The auxiliary agent For CeO2When, auxiliary agent presoma is cerous nitrate or ammonium ceric nitrate；The auxiliary agent is ZrO2When, auxiliary agent presoma is zirconium nitrate or nitre Sour oxygen zirconium；The auxiliary agent is CexZr1-xO2When, auxiliary agent presoma is any one in cerous nitrate, ammonium ceric nitrate and zirconium nitrate, nitre The mixture of any one in sour oxygen zirconium.
8. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 1, it is characterised in that：The load Body presoma is methyl silicate, ethyl orthosilicate, silicic acid propyl ester, butyl silicate, aluminium isopropoxide, aluminum nitrate, boehmite, titanium At least one of sour four butyl esters, isopropyl titanate.
9. the nickel-base catalyst of carbon dioxide pressurized reforming methane according to claim 1, it is characterised in that：The catalysis In the preparation method of agent, roasted 3~6 hours in 650~750 DEG C of air atmosphere.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112387285A (en) * 2020-11-03 2021-02-23 浙江海洋大学 Preparation method of nickel-based methane carbon dioxide reforming catalyst
CN112452328A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst
CN112452329A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 Synthesis method of reforming catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101352687A (en) * 2008-08-29 2009-01-28 同济大学 Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof
CN102240566A (en) * 2011-05-12 2011-11-16 太原理工大学 Preparation method of catalyst for preparing synthesis gas by reforming CH4/CO2
CN103977786A (en) * 2014-05-20 2014-08-13 陕西师范大学 Method for preparing CO2 oxidization ethylbenzene dehydrogenation catalyst by combustion decomposition method
CN105214658A (en) * 2014-05-29 2016-01-06 苏州工业园区新国大研究院 The Catalysts and its preparation method of synthesizing gas by reforming methane with co 2

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101352687A (en) * 2008-08-29 2009-01-28 同济大学 Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof
CN102240566A (en) * 2011-05-12 2011-11-16 太原理工大学 Preparation method of catalyst for preparing synthesis gas by reforming CH4/CO2
CN103977786A (en) * 2014-05-20 2014-08-13 陕西师范大学 Method for preparing CO2 oxidization ethylbenzene dehydrogenation catalyst by combustion decomposition method
CN105214658A (en) * 2014-05-29 2016-01-06 苏州工业园区新国大研究院 The Catalysts and its preparation method of synthesizing gas by reforming methane with co 2

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
EMMA C. LOVELL ET AL.: ""Flame spray pyrolysis-designed sillica/ceria-zirconia supports for the carbon dioxide reforming of merhane"", 《APPLIED CATALYSIS A,GENERAL》 *
HUA-PING REN ET AL.: ""Highly Active and Stable Ni-SiO2 Prepared by a Complex-Decomposition Method for Pressurized Carbon Dioxide Reforming of Methane"", 《IND. ENG. CHEM. RES.》 *
XIANMEI XIANG ET AL.: ""Nickel based mesoporous silica-ceria-zirconia composite for carbon dioxide reforming of methane"", 《APPLIED CATALYSIS A:GENERAL》 *
任琳等: ""CH4/CO2重整反应中NiO-CexZr1-xO2/Al2O3催化剂的研究"", 《广东化工》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112387285A (en) * 2020-11-03 2021-02-23 浙江海洋大学 Preparation method of nickel-based methane carbon dioxide reforming catalyst
CN112452328A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst
CN112452329A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 Synthesis method of reforming catalyst

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