CN106944159B - A kind of preparation method of catalyst for hydrogen production from methane vapor reforming - Google Patents
A kind of preparation method of catalyst for hydrogen production from methane vapor reforming Download PDFInfo
- Publication number
- CN106944159B CN106944159B CN201610003115.5A CN201610003115A CN106944159B CN 106944159 B CN106944159 B CN 106944159B CN 201610003115 A CN201610003115 A CN 201610003115A CN 106944159 B CN106944159 B CN 106944159B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- hydrogen
- nitrate
- active component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The present invention relates to a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst includes the following steps: to prepare catalyst precarsor B first, then reduction treatment is carried out to catalyst precarsor B, it is uniformly mixed with furfural aqueous solution by auxiliary agent presoma is soluble in water, then it is added in autoclave together with catalyst precarsor B, it is reacted after solution D is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.The catalyst reaction activity of this method preparation is high, not only reduces metal consumption, but also improve the selectivity of product.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst for hydrogen production from methane vapor reforming, more particularly, to a kind of methane water
The preparation method of vapour reforming hydrogen producing loading type nickel-based catalyst.
Background technique
Methane is the highest hydrocarbon molecules of hydrogen-carbon ratio, abundance in nature, can be used as excellent hydrogen feedstock.
Currently, mainly having hydrogen production from methane vapor reforming, partial oxidation of methane hydrogen, self-heating recapitalization by the hydrogen producing technology of raw material of methane
Hydrogen manufacturing etc..These types of technology typically obtains synthesis gas (H first2With the gaseous mixture of CO), then pass through conversion reaction (WGS)
And pressure-variable adsorption (PSA) obtains hydrogen.The wherein available hydrogen-carbon ratio (H of hydrogen production from methane vapor reforming2/ CO) be 3 synthesis
Gas, therefore be more suitable for for hydrogen manufacturing.Hydrogen production from methane vapor reforming is a kind of industrialization hydrogen producing technology of maturation, and process is inhaled by force
Heat usually carries out under the conditions of high temperature (800~1100 DEG C), operates (V using high steam/hydrocarbons ratioH2O/VCH4> 3), to prevent catalyst
Carbon deposit.Currently, high activity that the research of hydrogen production from methane vapor reforming is laid particular emphasis under the conditions of low steam carbon ratio and high stability are urged
Agent development, to seek to reduce the investment and the technical solution of production cost of natural gas steam reforming process.
Common SMR catalyst is loaded catalyst, carrier be aluminium oxide, zirconium oxide, cerium oxide,
Magnesia, lanthana, niobium oxide, zeolite, perovskite, silica clay, yttrium oxide, cobalt oxide, iron oxide and its mixture
One of or.Non-radioactive metal can be used as the active metal of SMR catalyst in group VIII.Studies have shown that
When group VIII noble metals Ru, Rh, Pd etc. are carried on suitable carrier, reactivity all with higher and anti-carbon
Can, but be that the shortcomings that noble metal expensive；In group VIII base metal, Raney nickel reaction with higher is lived
Property, generally use Ni/Al2O3Catalyst, reaction condition are 1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio between/CO is about 3.
Although existing catalyst can obtain preferable hydrogen production from methane vapor reforming reactivity worth, there are still costs
The problems such as higher, catalyst easy carbon distribution.Especially when reactant (methane and water) molecule mass transfer in catalyst granules, due to
The difference of diffusion velocity causes two kinds of reactant molecule ratios gradient, steam/hydrocarbons ratio inside particle radially occur in catalyst granules
Much smaller than stoichiometry, therefore carbon distribution is easier to inside catalyst granules.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of catalyst for hydrogen production from methane vapor reforming
Preparation method, the catalyst of this method preparation have the characteristics that low in cost, metal component utilization rate is high and selectivity is good.
The present invention provides a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes activity
Component, auxiliary agent and carrier, active component Ni, one or more of auxiliary agent Na, K, Mg, Ca, Sr, Ba, Zr, Ce, La are carried
Body is any one of aluminium oxide, silica, SBA-15；It is with the percentage that each element quality in catalyst accounts for catalyst quality
Benchmark, the content of active component are 10wt%~20wt%, and the content of auxiliary agent is 1wt%~5wt%, and surplus is carrier；The catalysis
The preparation method of agent includes the following steps:
(1) active component presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is obtained
Catalyst precarsor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
(3) the catalyst precarsor B obtained is added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added
It into autoclave described in step (4), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C；
(6) solidliquid mixture obtained to step (5) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added,
1~2h is placed, is then filtered, obtained solid sample after drying, calcination process, obtains catalyst again.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, active component forerunner described in step (1)
Body is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；In the solution A, active group
Divide based on the element, the mass fraction in solution A is 1%~7%.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, dipping described in step (2) is to wait bodies
Product dipping, dip time are 1~3h；The aging temperature be 10~90 DEG C, preferably 20~60 DEG C, ageing time be 1~
For 24 hours, preferably 4~12h；Drying temperature described in step (2) and step (6) is 70~150 DEG C, preferably 80~120 DEG C, is done
The dry time is 2~12h, preferably 4~8h；Maturing temperature described in step (2) and step (6) is 500~900 DEG C, preferably
600~800 DEG C, calcining time is 2~12h, preferably 4~8h.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, carrier described in step (2) is oxidation
Any one of aluminium, silica, SBA-15；The carrier can use commercially available product, can also be by side well known in the art
Method preparation；In the catalyst precarsor B, the nickel of load is 1wt%~5wt% of final catalyst in terms of element wt.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, reducing atmosphere described in step (3) is
The mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specifically
Reduction treatment process is as follows: catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then pass to hydrogen or hydrogen with
The mixed gas of nitrogen, in 0.1~0.5MPa(absolute pressure) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, auxiliary agent presoma described in step (4)
For sodium nitrate, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, nitre
One of sour cerium, lanthanum nitrate are a variety of, preferably magnesium nitrate；In the solution C, auxiliary agent based on the element, the matter in solution C
Measuring score is 1%~4%；The mass fraction of furfural is 30%~50% in the furfural aqueous solution；Furfural described in step (4) is water-soluble
Liquid and the mass ratio of solution C are 3~5, are urged after the reduction that the gross mass of the solution C and furfural aqueous solution is obtained with step (3)
The mass ratio of agent precursor B is 3~6.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, water soluble polymer described in step (5)
Polymer is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；The work
Property component presoma be one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；The solution
In D, in active component presoma the nickeliferous mass fraction in solution D based on the element be 0.3%~2%, water soluble polymer
Mass fraction of the polymer in solution D is 3~6 times of Ni element mass fraction.
In the preparation method of catalyst for hydrogen production from methane vapor reforming of the present invention, dehydrated alcohol is added described in (6) in step
Or the quality of citric acid and the mass ratio of water soluble polymer are 2~4；The mass fraction of the aqueous citric acid solution is
10%~20%.
The catalyst of the method for the present invention preparation can be applied to hydrogen production from methane vapor reforming reaction.Catalyst is before use
In a hydrogen atmosphere, 700~800 DEG C of 2~5h of prereduction.The catalyst of the method for the present invention preparation is applied to methane vapor reforming
Hydrogen production reaction, preferable process conditions are as follows: the composition H of unstripped gas2O/CH4Molar ratio is 1~4, in unstripped gas can containing Ar,
N2Or the dilution property gas such as He, 1000~3000h of unstripped gas air speed-1, reaction pressure be 0.2~3Mpa, reaction temperature be 600~
800℃。
Compared with prior art, a kind of available active metal outer layer distribution of the preparation method being related to through the invention
Catalyst for hydrogen production from methane vapor reforming.In the present invention, pre-soaked a part of active metal adds hydrogen to carry out furfural water phase
Reaction.Active metal predecessor and water soluble polymer is added simultaneously in the system of furfural hydrogenation, on the one hand utilizes
Furfural hydrogenation product hinders active metal to the diffusion inside catalyst granules；On the other hand, using active metal predecessor and
Coordination between water soluble polymer reduces concentration of the active metallic ion inside and outside catalyst granules in solution
Difference slows down active metal to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both reduces
Metal consumption, and improve the selectivity of product.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, prepares work
Skill is simple, is conducive to industrial amplification.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Evaluation condition: it is used hydrogen reducing 3 hours at 700 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
It is reacted in quartz reactor, 750 DEG C of reaction temperature, unstripped gas forms H2O/CH4/N2=6.75/2.25/1(molar ratio), it is empty
Fast 2000h-1, product is after condensation water removal with gas-chromatography on-line analysis.Reaction starts sampling analysis, evaluation knot after 1 ~ 3 hour
Fruit is shown in Table 1.Reaction result in table 1 is average activity of the catalyst after 750 DEG C of work 100h.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention
The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example
The scanning electron microscope analysis of component nickel the results are shown in Table 2.
Embodiment 1
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.2g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；6.41g magnesium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 12.7%Ni, and the catalyst of 1.9%Mg is denoted as C-1.
Embodiment 2
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.2g silica support (Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter 0.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；6.41g magnesium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 12.3%Ni, and the catalyst of 1.8%Mg is denoted as C-2.
Embodiment 3
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.2g SBA-15 carrier (Kong Rongwei 1.23mL/g, specific surface area 701m2/ g, bar shaped, equivalent diameter 1.5mm), at room temperature
2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h are impregnated, catalyst precarsor B is made, the Ni of load is in terms of element wt
The 3% of final catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is in mixed gas
80%, reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；6.41g magnesium nitrate is dissolved in 16mL deionized water,
Solution C is obtained, and the furfural aqueous solution for being 40% with the mass fraction of its 4 times of quality is uniformly mixed, then and after reduction activation
Catalyst precarsor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionization
In water, solution D is obtained；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts hydrogen pressure
Power reacts 2h at 150 DEG C to 3MPa；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and it is anhydrous that 33g is added
Ethyl alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, i.e.,
It is 12.9%Ni that quality based on the element, which is made, and accounts for catalyst percentage composition, and the catalyst of 2.1%Mg is denoted as C-3.
Embodiment 4
It weighs 0.99g nickel nitrate to be dissolved in 16mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
17.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 1% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；2.14g magnesium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；8.1g polyethylene glycol, 8.92g nickel nitrate are dissolved in 200mL deionized water,
Obtain solution D；Solution D is also added in autoclave, after sealing with hydrogen replace 3 times, then adjust Hydrogen Vapor Pressure to
3MPa reacts 2h at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 25g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 8.6%Ni, and the catalyst of 0.5%Mg is denoted as C-4.
Embodiment 5
It weighs 4.96g nickel nitrate to be dissolved in 11mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
13.2g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 5% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；10.68g magnesium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；13.5g polyethylene glycol, 14.87g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 41g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 17.3%Ni, and the catalyst of 3.7%Mg is denoted as C-5.
Embodiment 6
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；2.22g sodium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyvinylpyrrolidone (k30), 11.89g nickel nitrate are dissolved in
In 200mL deionized water, solution D is obtained；Solution D is also added in autoclave, after sealing with hydrogen replace 3 times, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25
DEG C, the aqueous citric acid solution that 220g mass fraction is 15% is added, places 1.5h, then filters, obtained solid sample is put into baking oven
In at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 12.2%Ni,
The catalyst of 1.9%Na, is denoted as C-6.
Embodiment 7
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.5g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；1.45g strontium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 4 times of quality be 40% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyvinyl alcohol, 11.89g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 165g mass is added
The aqueous citric acid solution that score is 20% is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry
6h roasts 6h at 700 DEG C, and obtaining quality based on the element and accounting for catalyst percentage composition is 12.4%Ni, the catalyst of 1.7%Sr,
It is denoted as C-7.
Embodiment 8
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；2.82g zirconium nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 3 times of quality be 30% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 12.5%Ni, and the catalyst of 2.1%Zr is denoted as C-8.
Embodiment 9
It weighs 2.97g nickel nitrate to be dissolved in 14mL deionized water, obtains solution A；It is carried on using equi-volume impregnating
15.4g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm), it soaks at room temperature
Catalyst precarsor B is made in stain 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, and the Ni of load is in terms of element wt, for most
The 3% of whole catalyst；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas,
Reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；1.87g lanthanum nitrate is dissolved in 16mL deionized water, is obtained
Solution C, and with the mass fraction of its 5 times of quality be 50% furfural aqueous solution be uniformly mixed, then with the catalysis after reduction activation
Agent precursor B is added in autoclave together；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water
In, obtain solution D；Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the anhydrous second of 33g is added
Alcohol is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 12.6%Ni, and the catalyst of 2.1%La is denoted as C-9.
Comparative example
Weigh 14.87g nickel nitrate, 6.41g magnesium nitrate is dissolved in deionized water, obtained aqueous solution；Using incipient impregnation
Method is carried on 15.2g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter 1.5mm),
2h, aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h are impregnated at room temperature, are obtained quality based on the element and are accounted for catalyst percentage and contain
Amount is 14.1%Ni, and the catalyst of 2.4%Mg is denoted as D-1.
The reactivity worth of 1 catalyst of table
2 catalyst activity component Ni content distribution (wt%) of table
Claims (24)
1. a kind of preparation method of catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and load
Body, active component Ni, one or more of auxiliary agent Na, K, Mg, Ca, Sr, Ba, Zr, Ce, La, carrier are aluminium oxide, oxygen
Any one of SiClx, SBA-15；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, active component
Content be 10wt%~20wt%, the content of auxiliary agent is 1wt%~5wt%, and surplus is carrier；The preparation method packet of the catalyst
Include following steps:
(1) active component presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is catalyzed
Agent precursor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) auxiliary agent presoma is soluble in water, solution C is obtained, and be uniformly mixed with furfural aqueous solution, is then obtained with step (3)
To catalyst precarsor B be added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step
Suddenly it in autoclave described in (4), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C, the water soluble polymer is polyethylene glycol (PEG), polyvinylpyrrolidone
(PVP), one or more of polyvinyl alcohol (PVA)；
(6) solidliquid mixture obtained to step (5) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, and places 1
~2h, is then filtered, and obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that: active component presoma described in step (1) be nickel nitrate,
One of nickel acetate, nickel sulfate, nickel chloride are a variety of.
3. according to the method for claim 1, it is characterised in that: active component presoma described in step (1) is nickel nitrate.
4. according to the method for claim 1, it is characterised in that: in solution A described in step (1), active component is with element
Meter, the mass fraction in solution A are 1%~7%.
5. according to the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10~90 DEG C, always
Change the time be 1~for 24 hours.
6. according to method described in claim 1 or 5, it is characterised in that: aging temperature described in step (2) is 20~60
DEG C, ageing time is 4~12h.
7. according to the method for claim 1, it is characterised in that: drying temperature described in step (2) and step (6) is 70~
150 DEG C, drying time is 2~12hh.
8. according to method described in claim 1 or 7, it is characterised in that: step (2) is with drying temperature described in step (6)
80~120 DEG C, drying time is 4~8h.
9. according to the method for claim 1, it is characterised in that: maturing temperature described in step (2) and step (6) is 500
~900 DEG C, calcining time is 2~12h.
10. according to method described in claim 1 or 9, it is characterised in that: step (2) is with maturing temperature described in step (6)
600~800 DEG C, calcining time is 4~8h.
11. according to the method for claim 1, it is characterised in that: in catalyst precarsor B described in step (2), load
Nickel is 1wt%~5wt% of final catalyst in terms of element wt.
12. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (3) is hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
13. according to the method for claim 1, it is characterised in that: auxiliary agent presoma described in step (4) be sodium nitrate,
Potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, cerous nitrate, nitric acid
One of lanthanum is a variety of.
14. according to method described in claim 1 or 13, it is characterised in that: auxiliary agent presoma described in step (4) is nitric acid
Magnesium.
15. according to the method for claim 1, it is characterised in that: in solution C described in step (4), auxiliary agent based on the element,
Mass fraction in solution C is 1%~4%.
16. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (4)
Score is 30%~50%.
17. according to the method for claim 1, it is characterised in that: the matter of furfural aqueous solution and solution C described in step (4)
Amount is than being 3~5.
18. according to the method for claim 1, it is characterised in that: solution C described in step (4) and furfural aqueous solution it is total
The mass ratio for the reduction rear catalyst precursor B that quality and step (3) obtain is 3~6.
19. according to the method for claim 1, it is characterised in that: active component presoma described in step (5) is nitric acid
One of nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
20. according to method described in claim 1 or 19, it is characterised in that: active component presoma described in step (5) is nitre
Sour nickel.
21. according to the method for claim 1, it is characterised in that: in solution D described in step (5), active component presoma
Middle the nickeliferous mass fraction in solution D based on the element is 0.3%~2%.
22. according to the method for claim 1, it is characterised in that: water soluble polymer described in step (5) is molten
Mass fraction in liquid D is 3~6 times of Ni element mass fraction.
23. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (6)
The mass ratio of quality and water soluble polymer is 2~4.
24. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (6)
It is 10%~20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610003115.5A CN106944159B (en) | 2016-01-07 | 2016-01-07 | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610003115.5A CN106944159B (en) | 2016-01-07 | 2016-01-07 | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944159A CN106944159A (en) | 2017-07-14 |
| CN106944159B true CN106944159B (en) | 2019-01-25 |
Family
ID=59465153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610003115.5A Active CN106944159B (en) | 2016-01-07 | 2016-01-07 | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944159B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866261B (en) * | 2017-11-14 | 2020-10-27 | 北京赛诺时飞石化科技有限公司 | Hydrocarbon reforming catalyst of modified SBA-15 molecular sieve and preparation method and application thereof |
| CN110586111A (en) * | 2019-09-17 | 2019-12-20 | 大连海事大学 | Preparation method of composite catalyst for hydrogen production by methane steam reforming |
| CN111545215B (en) * | 2020-06-22 | 2022-09-30 | 中国科学技术大学 | Perovskite-loaded monatomic catalyst and preparation method and application thereof |
| CN112916015B (en) * | 2021-01-27 | 2022-07-01 | 成都理工大学 | Strontium-zirconium perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114772552A (en) * | 2022-03-23 | 2022-07-22 | 浙江浙能技术研究院有限公司 | Structured oxygen carrier for hydrogen production by chemical chain methane reforming and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139897A (en) * | 1978-04-22 | 1979-10-30 | Jgc Corp | Low temperature steam reforming catalyst for hydrocarbon |
-
2016
- 2016-01-07 CN CN201610003115.5A patent/CN106944159B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944159A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106944159B (en) | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming | |
| CN106944060B (en) | A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst | |
| CN102886272A (en) | Supported catalyst, preparation method and application thereof | |
| CN105727955B (en) | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming | |
| CN109718770B (en) | Catalyst carrier, supported catalyst, preparation method and application of supported catalyst, and methane combined reforming method | |
| CN105727978B (en) | A kind of method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation | |
| CN105642290B (en) | A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst | |
| CN105727972B (en) | A kind of method for preparing catalyst for synthesizing gas by reforming methane with co 2 | |
| CN106475103B (en) | A kind of preparation method of methane portion oxidation synthesis gas catalyst | |
| CN105727954B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN106475106B (en) | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst | |
| Wei et al. | Hydrogenation of pentenal over supported Pt nanoparticles: Influence of Lewis-acid sites in the conversion pathway | |
| CN109718763B (en) | Carrier, supported catalyst, preparation method and application of supported catalyst, and method for preparing synthesis gas by dry reforming of methane | |
| CN106944078B (en) | A kind of preparation method for catalyst for hydrogen production from methane vapor reforming | |
| CN110329992A (en) | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof | |
| CN105642288B (en) | A kind of preparation method of methane portion oxidation synthesis gas catalyst | |
| CN106944059B (en) | A kind of preparation method of synthesis gas full methanation catalyst | |
| CN106944062B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN108654637A (en) | A kind of cobalt-base catalyst and preparation method and application and Fischer-Tropsch synthesis method | |
| CN106944082B (en) | A kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst | |
| CN106944071B (en) | The preparation method of methane portion oxidation synthesis gas catalyst | |
| CN109908907B (en) | Catalyst for reforming methane and carbon dioxide to produce synthetic gas and its preparing process | |
| CN106944061B (en) | A kind of preparation method of synthesis gas methanation catalyst | |
| CN106944068B (en) | A kind of preparation method for methane portion oxidation synthesis gas catalyst | |
| CN105642305B (en) | A kind of method for preparing catalyst for hydrogen production from methane vapor reforming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |