CN105727976B - A kind of method for preparing catalyst for methane portion oxidation synthesis gas - Google Patents
A kind of method for preparing catalyst for methane portion oxidation synthesis gas Download PDFInfo
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- CN105727976B CN105727976B CN201410732129.1A CN201410732129A CN105727976B CN 105727976 B CN105727976 B CN 105727976B CN 201410732129 A CN201410732129 A CN 201410732129A CN 105727976 B CN105727976 B CN 105727976B
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Abstract
The present invention relates to a kind of method for preparing catalyst for methane portion oxidation synthesis gas, the catalyst includes active component, auxiliary agent and carrier, and the method for preparing catalyst includes：Catalyst precarsor A is made in processing waste residue oil hydrogenation catalysts；Then reduction treatment is carried out to catalyst precarsor A using reducing atmosphere；Catalyst precarsor A after reduction and polyhydric alcohol solutions are added in autoclave and carry out hydrogenation reaction, reaction effluent is placed and then filtered and is dry, obtains catalyst precarsor B；Active component presoma is soluble in water, solution C is obtained, catalyst precarsor B is then added in, after drying, calcination process, obtains catalyst.The method of the present invention not only takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, and promotes dispersion of the more multiple active components in carrier surface, has not only improved the utilization rate of active metal, but also improve the conversion ratio of methane and the selectivity of product.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst for methane portion oxidation synthesis gas, more particularly, to one kind
For the loading type nickel-based catalyst preparation method of methane portion oxidation synthesis gas.
Background technology
More than 90% gas component is methane, is natural gas profit by methane through synthesis gas synthetic fuel and chemicals again
One of effective way.With traditional vapour reforming ratio, methane portion oxidation synthesis gas has required reaction vessel body
The advantages that small, reaction rate of product is fast, low energy consumption and the synthesis gas of generation is suitable as the unstripped gas of methanol and Fiscber-Tropscb synthesis.Separately
Outside, methane portion oxidation technology is developed it is possible that replacing highly endothermic methane steam reformation technique for producing synthesis gas, it is special
It is not to be of great significance for remote or offshore natural gas resource utilization.
The main catalyst system of methane portion oxidation synthesis gas is by active component noble metal（Pt, Pd, Rh, Ru,
Ir）, nickel or cobalt be supported on the carriers such as aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, while can be used alkali metal,
Alkaline-earth metal or rare-earth oxide are modified the reactivity worth to improve catalyst.
CN 101049566A disclose a kind of for the Ni bases catalyst of methane portion oxidation synthesis gas and its preparation side
Method.The carrier of catalyst is complex carrier Mg-Al-Ce-Zr-O, active component NiO.The patent is made using coprecipitation method
Obtained carrier is dipped in Ni (NO by complex carrier3)2In solution, methane conversion reaches more than 84%, CO on obtained catalyst
Selectivity reaches more than 99%.
CN 101219393A disclose a kind of cobalt-based loaded catalyst for methane portion oxidation synthesis gas and its
Preparation method.Catalyst takes step impregnation method to prepare, using Co as active component, using a kind of alkaline-earth metal or rare earth metal to help
Agent, using HZSM-5 as carrier, catalyst activity obtained is high, coking resistivity is strong, stability is good.
CN 101284241A disclose a kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof.With mistake
It is active component that metal Co, which is crossed, with noble metal, using a kind of element selected from alkaline-earth metal as auxiliary agent, with γ-Al2O3For carrier, adopt
The catalyst of methane portion oxidation synthesis gas is made with infusion process.Catalyst has high activity, excellent coking resistivity, Gao Wen
The advantages of qualitative.
Although catalyst made from above-mentioned patented method obtains preferable methane portion oxidation synthesis gas reactivity
Can, but since the reaction is a fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）,
Reactant reacts while catalyst external surface is reached have been completed, thus the inner surface of catalyst contributes not goal response
Greatly, this has resulted in rate of metal relatively low in carrier duct, while can also accelerate the deep oxidation of product.
Invention content
To overcome shortcoming of the prior art, the present invention provides a kind of for methane portion oxidation synthesis gas
Method for preparing catalyst, catalyst prepared by this method have that of low cost, metal component utilization rate is high, good, the anti-product of selectivity
Charcoal ability is strong and the characteristics of stability is good.
The preparation method of methane portion oxidation synthesis gas catalyst of the present invention, the catalyst include activearm
Point, auxiliary agent and carrier, active component Ni；Auxiliary agent is one or more of Co, Mo or V, and carrier is aluminium oxide；With catalyst
Middle each element quality is accounted on the basis of the percentage of catalyst quality, and the content of active component is 10wt%~30wt%, preferably 15wt%
~25wt%, the content of auxiliary agent is 1wt%~15wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps：
（1）Useless hydrotreating catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C dry, is carried out
Calcination process obtains catalyst precarsor A, and the calcination temperature is 300 ~ 600 DEG C, and roasting time is 2~6h；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）By step（2）Catalyst precarsor A after obtained reduction is added to polyhydric alcohol solutions in autoclave,
It is replaced 2~5 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；
（4）By step（3）Obtained reaction effluent places 1~3h, then filters, obtained solid sample at room temperature into
Row drying, until sample surfaces without liquid phase, obtain catalyst precarsor B；
（5）Active component presoma is soluble in water, solution C is obtained, then adds in step（4）Obtained catalyst precarsor
B after drying, calcination process, obtains catalyst.
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, step（1）At the useless plus hydrogen
Reason catalyst refers to former reaction requirement being not achieved or due to grading without the fixed bed of complete deactivation or boiling
The catalyst for hydrotreatment of residual oil used on bed is risen, generally residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating is urged
Agent.For the useless hydrotreating catalyst using aluminium oxide as carrier, active metal component contains Mo and Co, and described giving up adds at hydrogen
Catalyst is managed due to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, generally has portion
Divide W metal and V depositions.
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, step（1）The catalyst
The content of Mo is 5wt% ~ 15wt% in precursor A, and the content of Co is 1wt% ~ 3wt%, and the content of V is 1wt% ~ 3wt%, and the content of Ni is
1wt%~5wt%。
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, step（2）Described in reduction
Atmosphere is hydrogen or the mixed gas of hydrogen and nitrogen, and hydrogen volume content is 10%~95% in the mixed gas.Specifically
Reduction treatment process it is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen
With the mixed gas of nitrogen, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, it is down to room temperature in a nitrogen atmosphere.
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, step（3）Described in it is polynary
Alcohol can be one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%
~10%；The polyhydric alcohol solutions and step（2）The obtained volume ratio of reduction rear catalyst precursor A is 5~10.
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, step（5）Described in activity
Component presoma is the soluble-salt of Ni, is specifically as follows nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or
Nickel acetate；A concentration of 0.5~3.5mol/L of active component nickel in the solution C.The specific dipping process of active component is adopts
With method well known to those skilled in the art.The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is
2~12h, preferably 4~8h.The calcination temperature is 350~650 DEG C, preferably 400~600 DEG C, roasting time for 2~
12h, preferably 4~8h.
Catalyst prepared by the method for the present invention can also need to be made suitable particle shape according to what is used, and item is such as made
Shape, piece shape, cylindricality etc..
Catalyst prepared by the method for the present invention can be applied to methane portion oxidation synthesis gas reaction.Catalyst is using
It is preceding in a hydrogen atmosphere, 700~800 DEG C of 1~3h of prereduction.Catalyst prepared by the method for the present invention is applied to methane portion oxidation
Preparing synthetic gas reacts, and preferable process conditions are：The composition CH of unstripped gas4/O2Molar ratio is 1.75~2.2, can be in unstripped gas
Contain Ar, N2Or the dilution such as He property gas, 20000~200000h of unstripped gas air speed-1, reaction pressure is 0.1~1Mpa, is reacted
Temperature is 600~900 DEG C.
Mo, Co, V, Ni metal in waste residue oil hydrogenating treatment catalyst is utilized, simultaneously in catalyst of the present invention
Also the alumina catalyst support of dead catalyst is taken full advantage of, the comprehensive utilization of metal and carrier is realized, has saved cost；It is processed
Dead catalyst as catalyst precarsor, after reduction treatment, catalytic polyol water phase adds hydrogen in autoclave, generation
Product C5And C6Liquid alkane can be further processed catalyst precarsor as atent solvent；Catalyst after treatment
Precursor load active component nickel again preferably controls the active metal amount loaded in carrier duct, promotes more activearms
Point carrier surface dispersion, both improved the utilization rate of active metal, and reduced catalyst cost, but accelerate reactant and
Adsorption desorption speed of the product in catalyst surface and hole so as to avoid the further oxidation of product, improves turning for methane
The selectivity of rate and product.
Specific embodiment
The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.
Evaluation condition：With hydrogen reducing 2 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 composition CH4/O2/Ar = 2/1/4（Molar ratio）, air speed 1 ×
105h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Sampling analysis after reaction 1 hour, evaluation results are shown in Table 1.
Using point of active component in the catalyst prepared by the scanning electron microscope analysis present invention and auxiliary agent on a catalyst
Cloth situation.The scanning electron microscope analysis of catalyst activity component nickel the results are shown in Table 2 obtained by the embodiment of the present invention.
Embodiment 1
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；Catalyst precarsor A after reduction activation and 300mL mass concentrations are added in for 10% sorbitol solution
It into autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will
Mixture after being reacted in above-mentioned autoclave places 2h, filtering, and obtained solid sample is dried at room temperature for sample surfaces aneroid
Phase obtains catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 20%Ni, 6.73%Mo, 1.47%Co, and the catalyst of 1.62%V is denoted as C-1.
Embodiment 2
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；Catalyst precarsor A after reduction activation and 300mL mass concentrations are added in for 10% sorbitol solution
It into autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will
Mixture after being reacted in above-mentioned autoclave places 2h, filtering, and obtained solid sample is dried at room temperature for sample surfaces aneroid
Phase obtains catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 31.16g nickel nitrates, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 30%Ni, 5.58%Mo, 1.22%Co, and the catalyst of 1.35%V is denoted as C-2.
Embodiment 3
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；Catalyst precarsor A after reduction activation and 300mL mass concentrations are added in for 10% sorbitol solution
It into autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will
Mixture after being reacted in above-mentioned autoclave places 2h, filtering, and obtained solid sample is dried at room temperature for sample surfaces aneroid
Phase obtains catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 14.94g nickel nitrates, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 15%Ni, 7.3%Mo, 1.6%Co, and the catalyst of 1.76%V is denoted as C-3.
Embodiment 4
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；Catalyst precarsor A after reduction activation and 400mL mass concentrations are added in for 10% xylitol solution
It into autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will
Mixture after being reacted in above-mentioned autoclave places 2h, filtering, and obtained solid sample is dried at room temperature for sample surfaces aneroid
Phase obtains catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 20%Ni, 6.73%Mo, 1.47%Co, and the catalyst of 1.62%V is denoted as C-4.
Embodiment 5
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；Catalyst precarsor A after reduction activation and 200mL mass concentrations are added in for 10% mannitol solution
It into autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will
Mixture after being reacted in above-mentioned autoclave places 2h, filtering, and obtained solid sample is dried at room temperature for sample surfaces aneroid
Phase obtains catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, in 80 DEG C of stirrings extremely
Solution is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst
Percentage composition is 20%Ni, 6.73%Mo, 1.47%Co, and the catalyst of 1.62%V is denoted as C-5.
Embodiment 6
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；The sorbitol solution that catalyst precarsor A and 300mL mass concentrations after reduction activation are 5% is added to
It in autoclave, is replaced 3 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 3MPa, react 4h at 220 DEG C；It will be upper
It states the mixture after being reacted in autoclave and places 2h, filtering, obtained solid sample is dried at room temperature for sample surfaces without liquid phase,
Obtain catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, is stirred in 80 DEG C to molten
Liquid is evaporated, and is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element and account for catalyst hundred
It is 20%Ni, 6.73%Mo, 1.47%Co to divide content, and the catalyst of 1.62%V is denoted as C-6.
Comparative example 1
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is added
Enter to 50mLC6In alkane solvent, 20min is impregnated, then filters, is dried at room temperature for, until precursor surface is made without liquid phase
Catalyst precarsor B；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, is steamed in 80 DEG C of stirrings to solution
It is dry, dry 12h is put into baking oven at 110 DEG C, 4h is roasted at 400 DEG C, quality based on the element is obtained and accounts for catalyst percentage and contain
It measures as 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V is denoted as D-1.
Comparative example 2
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is added
Enter in the sorbitol solution for being 10% to 300mL mass concentrations, impregnate 20min, then filter, be dried at room temperature for, until precursor
Catalyst precarsor B is made without liquid phase in surface；Catalyst precarsor B is added in the aqueous solution containing 22.84g nickel nitrates, in 80
DEG C stirring is evaporated to solution, is put into baking oven at 110 DEG C dry 12h, is roasted 4h at 400 DEG C, obtain quality based on the element
Catalyst percentage composition is accounted for as 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V is denoted as D-2.
Comparative example 3
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8 h, gained catalyst roasts 4h at 450 DEG C, obtains catalyst precarsor A, wherein
Mo accounts for catalyst precarsor A weight 8.7wt%, Co and accounts for catalyst precarsor A weight 1.9wt% based on the element based on the element, and Ni is with element
Meter accounts for catalyst precarsor A weight 2.8wt%, V and accounts for catalyst precarsor A weight 2.1wt% based on the element；20g catalyst precarsors A is added
Enter into the aqueous solution containing 22.84g nickel nitrates, be evaporated in 80 DEG C of stirrings to solution, is put into baking oven at 110 DEG C dry
12h roasts 4h at 400 DEG C, obtains quality based on the element and accounts for catalyst percentage composition as 20%Ni, 6.73%Mo, 1.47%Co,
The catalyst of 1.62%V, is denoted as D-3.
The reactivity worth of 1 catalyst of table
2 catalyst activity component nickel content of table is distributed（wt%）
Claims (16)
1. a kind of preparation method of methane portion oxidation synthesis gas catalyst, the catalyst include active component, auxiliary agent and
Carrier, active component Ni；Auxiliary agent is one or more of Co, Mo or V, and carrier is aluminium oxide；With each element in catalyst
Quality is accounted on the basis of the percentage of catalyst quality, and the content of active component is 10wt%~30wt%, and the content of auxiliary agent is 1wt%
~15wt%, surplus are carrier；The preparation method of the catalyst includes the following steps：
（1）Useless hydrotreating catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C dry, is roasted
Processing obtains catalyst precarsor A, and the calcination temperature is 300 ~ 600 DEG C, and roasting time is 2~6h；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）By step（2）Catalyst precarsor A after obtained reduction is added to polyhydric alcohol solutions in autoclave, is sealed
It is replaced 2~5 times with hydrogen afterwards, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C, described is more
First alcohol is one or more in xylitol, sorbierite, mannitol, arabite；
（4）By step（3）Obtained reaction effluent places 1~3h, then filters, obtained solid sample is done at room temperature
It is dry, until sample surfaces without liquid phase, obtain catalyst precarsor B；
（5）Active component presoma is soluble in water, solution C is obtained, then adds in step（4）Obtained catalyst precarsor B, warp
After dry, calcination process, catalyst is obtained.
2. according to the method for claim 1, it is characterised in that：The content of the active component is 15wt%~25wt%.
3. according to the method for claim 1, it is characterised in that：Step（1）Described in useless hydrotreating catalyst be slag
Oil hydrogenating treatment catalyst.
4. according to the method for claim 3, it is characterised in that：Step（1）Described in useless hydrotreating catalyst be slag
Oily Hydrobon catalyst and/or residuum hydrogenating and metal-eliminating catalyst.
5. according to method any one of Claims 1-4, it is characterised in that：Step（1）Described in useless hydrotreating
For catalyst using aluminium oxide as carrier, active metal component contains Mo and Co.
6. according to the method for claim 1, it is characterised in that：Step（1）Described in catalyst precarsor A in Mo content
For 5wt% ~ 15wt%, the content of Co is 1wt% ~ 3wt%, and the content of V is 1wt% ~ 3wt%, and the content of Ni is 1wt% ~ 5wt%.
7. according to the method for claim 1, it is characterised in that：Step（2）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume content is 10%~95% in the mixed gas.
8. according to the method for claim 1, it is characterised in that：Step（2）Described in reduction treatment process it is as follows：Nitrogen
Catalyst precarsor A is warming up to 300~600 DEG C under atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, 0.1
After~0.5MPa handles 4~8h, it is down to room temperature in a nitrogen atmosphere.
9. according to the method for claim 1, it is characterised in that：Step（3）Described in polyhydric alcohol solutions mass concentration
It is 5%~10%.
10. according to the method for claim 1, it is characterised in that：Step（3）Described in polyhydric alcohol solutions and step（2）
The obtained volume ratio of reduction rear catalyst precursor A is 5~10.
11. according to the method for claim 1, it is characterised in that：Step（5）Described in active component presoma be Ni
Soluble-salt.
12. according to the method for claim 11, it is characterised in that：Step（5）Described in active component presoma be nitre
Sour nickel, nickel acetate, nickel sulfate or nickel chloride.
13. according to the method for claim 12, it is characterised in that：Step（5）Described in active component presoma be nitre
Sour nickel or nickel acetate.
14. according to the method for claim 1, it is characterised in that：A concentration of the 0.5 of active component nickel in the solution C~
3.5mol/L。
15. according to the method for claim 1, it is characterised in that：The drying temperature is 70~150 DEG C, drying time 2
~12h, the calcination temperature are 350~650 DEG C, and roasting time is 2~12h.
16. according to the method for claim 15, it is characterised in that：The drying temperature is 80~120 DEG C, and drying time is
4~8h, the calcination temperature are 400~600 DEG C, and roasting time is 4~8h.
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| CN201410732129.1A CN105727976B (en) | 2014-12-06 | 2014-12-06 | A kind of method for preparing catalyst for methane portion oxidation synthesis gas |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1484108A1 (en) * | 2003-06-06 | 2004-12-08 | L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude | Supported catalyst for producing H2 and/or CO from low molecular weight hydrocarbons |
| CN1994561A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing synthetic gas by partial oxidation of methane and method for preparing same |
| CN101049566A (en) * | 2007-05-23 | 2007-10-10 | 天津大学 | Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN103801296A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of nickel-based catalyst for syngas preparation by methane partial oxidation |
Family Cites Families (1)
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|---|---|---|---|---|
| JP4333976B2 (en) * | 2000-03-08 | 2009-09-16 | 財団法人 ひろしま産業振興機構 | Catalyst for partial oxidation of methane, method for producing the same, and method for producing synthesis gas using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1484108A1 (en) * | 2003-06-06 | 2004-12-08 | L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude | Supported catalyst for producing H2 and/or CO from low molecular weight hydrocarbons |
| CN1994561A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing synthetic gas by partial oxidation of methane and method for preparing same |
| CN101049566A (en) * | 2007-05-23 | 2007-10-10 | 天津大学 | Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN103801296A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of nickel-based catalyst for syngas preparation by methane partial oxidation |
Non-Patent Citations (1)
| Title |
|---|
| "甲烷部分氧化制取合成气镍基催化剂及工艺研究";宫立倩;《中国优秀硕士学位论文全文数据库工程科技I辑》;20060615(第6期);苯9-55 * |
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