CN108295905A - A kind of surfactant enhancing CO2The preparation method and application of reforming catalyst - Google Patents
A kind of surfactant enhancing CO2The preparation method and application of reforming catalyst Download PDFInfo
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- CN108295905A CN108295905A CN201810119620.5A CN201810119620A CN108295905A CN 108295905 A CN108295905 A CN 108295905A CN 201810119620 A CN201810119620 A CN 201810119620A CN 108295905 A CN108295905 A CN 108295905A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000002407 reforming Methods 0.000 title claims abstract description 21
- 230000002708 enhancing effect Effects 0.000 title claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 210000002966 serum Anatomy 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 13
- 238000009776 industrial production Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- B01J35/617—
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- B01J35/635—
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- B01J35/647—
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of surfactants to enhance CO2The preparation method and application of reforming catalyst.Claim the tetrapropylammonium hydroxide (TPAOH) of metering ratio in suitable distilled water first, be stirred overnight, until being completely dissolved；Then Ni (the NO of metering are weighed3)2·6H2(with the gross mass of carrier and active component Ni for 100%, in catalyst 10%) mass percent of active component Ni is is added in surfactant solution to O, and stirring and dissolving, waits for Ni (NO3)2·6H2After O is completely dissolved, 41 molecular sieves of MCM of metering are added, impregnate 45min；Above-mentioned mixed serum water bath method at 80 DEG C, 110 DEG C of dry 12h, 4h is roasted at 550 DEG C, surfactant-modified 10%Ni/MCM 41 TPAOH (1/x) catalyst is prepared (wherein 1/x indicates the molar ratio of above-mentioned TPAOH and Ni).The high temperature active and low temperature active of catalyst prepared by this method have more apparent raising, and simple for process, and preparation condition is easily controllable, are suitble to industrial production.
Description
Technical field
The invention belongs to CO2A kind of methane reforming reaction field, and in particular to surfactant enhancing CO2Reforming catalyst
Preparation method and application.
Background technology
With the getting worse of petroleum resources increasingly depleted and environmental pollution, cleaning, cheap fuel money are developed and utilized
Source by various countries common concern.Research methane carbon dioxide reformation can not only comprehensively utilize abundant natural gas and titanium dioxide
Carbon resource effectively alleviates CH4、CO2Caused greenhouse effects mitigate atmosphere pollution；Two kinds of greenhouse gases can be converted simultaneously
For the huge synthesis gas (CO/H of application value2≈1).And the process is rich in CO2Gas field it is particularly suitable, can reduce point
From CO2Expense.Therefore, the life that the R and D of the process utilize high efficiency of energy, reduce greenhouse gases, protecting the mankind
Dis environment has positive effect.
Lot of documents research shows that group VIII transition metal all has reforming activity (in addition to Os), wherein noble metal Ru,
The catalyst such as Rh, Ir, Pd, Re, Pt have higher activity and coking resistivity, especially best with former three catalytic performance.But
Noble metal is expensive and resource is limited, is not suitable for industrialization.Base metal became reforming methane with carbon dioxide activity in recent years
The research hotspot of component is concentrated mainly on Ni, Fe, Co, Cu etc..The wherein reforming activity of Ni bases catalyst is close to precious metal catalyst
Agent, and relative low price, therefore have become the hot spot of the current repercussion study.
Chinese patent CN 102658145A disclose a kind of preparation method of MgO (111) supported nickel based catalysts.First
Magnesium rod is dissolved in absolute ethyl alcohol by step, sequentially adds methoxy benzyl alcohol, ethyl alcohol, is reacted, is roasted in autoclave reaction
To carrier；Second step will obtain catalyst in carrier impregnation and nickel acetylacetonate solution.The reforming reaction activity of catalyst is better than
Conventional Al2O3The nickel-base catalyst of load.But the preparation process complex process of the catalyst, process are not easy to control.
Chinese patent CN 1280882A disclose a kind of nickel-base catalyst of nano-crystal oxide load.One is configured first
Determine the zirconium oxychloride aqueous solution of concentration, the ammonium hydroxide for diluting 2-15 times is added dropwise thereto as precipitating reagent, control ph is continuously stirred
It mixes, then deionization washs, and filters or be centrifugally separating to obtain the zirconium hydroxide hydrosol, then absolute ethyl alcohol washs to obtain alcogel,
Using supercritical drying, N2Nano-crystal oxide is obtained after atmosphere roasting, nickel nitrate aqueous solution is finally added to nanocrystal
In oxide, catalyst is made in stirring, dry, roasting.The reaction of the catalyst lasts a long time, at 757 DEG C, CO2And CH4Conversion
Rate all reaches 80% or more, but preparation process is complicated, and cost is higher.
He et al. (CO2reforming of methane to syngas over highly-stable Ni/SBA-
15catalysts prepared by P123-assisted method[J].International journal of
hydrogen energy,2016,41(3):1513-1523.) surfactant P123 is used to prepare carrier S BA-15, then added
Ni/SBA-15 catalyst is made in P123 and nickel nitrate aqueous solution co-impregnation SBA-15, water-bath, drying, roasting.The catalyst is urged
Change activity and stability is significantly improved.However the price of surfactant P123 and SBA-15 manufacturing costs are all more high
It is expensive, therefore industrialization relatively difficult to achieve.
Although catalyst made from above-mentioned patented method and literature method obtains preferable CO 2 reformation system and closes
At solid/liquid/gas reactions performance, but there are still cost is higher, preparation process is complicated, be difficult to industrialize the problems such as.Therefore, prepared by research
Reforming catalyst that is simple for process, inexpensive, haveing excellent performance becomes emphasis.The present invention is by the surfactant application of relative moderate
In support type Ni/MCM-41 catalyst prepared by conventional impregnation method, research is surfactant-modified to molecular sieve MCM-41 carriers
The active influence of structure and Reforming catalyst of the nickel-base catalyst supported, is rarely reported at present.
Invention content
The purpose of the present invention is to provide a kind of surfactants to enhance CO2The preparation method and application of reforming catalyst.
This method has advantage simple for process, easy to operate, at low cost.Pass through the surfactant-modified reforming catalyst being prepared
Have more preferable reactivity and yield.To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of surfactant enhancing CO2The preparation method of reforming catalyst includes the following steps：
A, by n (TPAOH):N (Ni)=1:100-1:5 surfactant tetrapropylammonium hydroxide (TPAOH) is dissolved in quantitative steaming
In distilled water, stirring obtains surfactant solution until being completely dissolved；
B, by the Ni (NO of metering3)2·6H2O (with the gross mass of carrier and active component Ni for 100%, activearm in catalyst
It is 10%) to be added in the surfactant solution that a steps obtain to divide the mass percent of Ni, and stirring obtains until being completely dissolved
Mixed solution；
C, in the mixed solution for obtaining the MCM-41 molecular sieves of metering addition b step, dipping obtains mixed serum；
D, the mixed serum that step c obtains is placed in water-bath, water bath method obtains dried powder；
E, the dried powder that Step d obtains is put in an oven, it is dry, obtain catalyst runic；
F, the catalyst runic that step e obtains is placed in Muffle furnace, is roasted to get surfactant-modified 10%Ni/MCM-
41-TPAOH (1/x) catalyst (wherein 1/x indicates the molar ratio of above-mentioned TPAOH and Ni).
According to said program, the surfactant is tetrapropylammonium hydroxide (TPAOH).
According to said program, the additive amount of the surfactant is n (TPAOH):N (Ni)=1:50-1:5.
According to said program, in order to reach better CO 2 reformation preparing synthetic gas reactivity worth, preferably surface-active
Agent additive amount is n (TPAOH):N (Ni)=1:50.
It is described to carry according to said program according to said program, with the gross mass of carrier and active component nickel for 100%, urge
The mass fraction of active component Ni is 10% in agent.
Compared with prior art, carrier is MCM-41 molecular sieves.
The invention has the advantages that：
(1) surfactant of the invention enhances CO2Reforming catalyst is used for CO2/CH4Reforming reaction, reaction temperature exist
Within the scope of 500 DEG C -800 DEG C, all more unmodified catalyst of reactivity and yield of catalyst is significantly improved.It lives on surface
Property agent tetrapropylammonium hydroxide additive amount be n (TPAOH):N (Ni)=1:When 50, catalyst reformation performance is best, 800 DEG C
When, the conversion ratio of reactor feed gas (methane and carbon dioxide) is all up to 85% or more, and carbon monoxide yield is better than 83%.Two
17% and 14% or more has been respectively increased than unmodified catalyst in person.
(2) preparation method is simple for process, and preparation condition is easily controllable, is suitble to industrial production.
Description of the drawings
Fig. 1 is embodiment 1, the catalytic activity test chart of example 2, example 3,6 prepared catalyst of example 4, example 5 and comparative example.
Fig. 2 is the XRD spectra of 6 prepared catalyst of embodiment 3 and comparative example.
Fig. 3 is the TPR table sign figure of 6 prepared catalyst of embodiment 3 and comparative example.
Fig. 4 is the BET phenograms of 6 prepared catalyst of embodiment 3 and comparative example.
Specific implementation mode
Below by some embodiments, the invention will be further described, but is not so limited the present invention.
The preparation of embodiment 1 10%Ni/MCM-41-TPAOH (1/100) catalyst
0.02757g tetrapropylammonium hydroxide (TPAOH) is weighed in 30ml distilled water, is stirred overnight, until completely molten
Solution；Then by 0.9858gNi (NO3)2.6H2O is added in surfactant solution, stirring and dissolving；Finally again by 1.8gMCM-41
Molecular sieve carrier is added in above-mentioned mixed solution, stirs evenly, room temperature immersion 45min；By above-mentioned mixed serum in 80 DEG C of water-baths
It is evaporated, 110 DEG C of dry 12h roast 4h at 550 DEG C, obtain addition surfactant n (TPAOH):N (Ni)=1:100
10%Ni/MCM-41-TPAOH (1/100) catalyst.
The evaluation of catalyst
The activity rating of catalyst carries out in self-control continuous fixed bed reactor.Reaction tube is an internal diameter 6mm, length
The quartz ampoule of 33cm, reaction temperature are measured by being placed in the thermocouple among reaction tube, and are controlled instead using temperature programming controller
Answer temperature.Gas flow is controlled by mass flowmenter, and air speed is 36000ml/ (gcatMin), reaction temperature is 500 DEG C -800
DEG C, every 50 DEG C of samplings.It is detected online with gas chromatographicanalyzer.Catalytic performance curve of the catalyst in different temperature points
Figure is as shown in Figure 1.
The preparation of embodiment 2 10%Ni/MCM-41-TPAOH (1/75) catalyst
Compared with Example 1, only surfactant TPAOH additive amounts are different, n (TPAOH):N (Ni)=1:75, be
0.03676g, other operating process are same as Example 1, and 10%Ni/MCM-41-TPAOH (1/75) catalyst is prepared.
The evaluation of catalyst
By the evaluation method of case study on implementation 1, catalyst is as shown in Figure 1 in the catalytic performance curve graph of different temperature points.
The preparation of embodiment 3 10%Ni/MCM-41-TPAOH (1/50) catalyst
Compared with Example 1, only surfactant TPAOH additive amounts are different, n (TPAOH):N (Ni)=1:50, be
0.0551g, other operating process are same as Example 1, and 10%Ni/MCM-41-TPAOH (1/50) catalyst is prepared.
The evaluation of catalyst
By the evaluation method of case study on implementation 1, catalyst is as shown in Figure 1 in the catalytic performance curve graph of different temperature points.
The preparation of embodiment 4 10%Ni/MCM-41-TPAOH (1/25) catalyst
Compared with Example 1, only surfactant TPAOH additive amounts are different, n (TPAOH):N (Ni)=1:25, be
0.1103g, other operating process are same as Example 1, and 10%Ni/MCM-41-TPAOH (1/25) catalyst is prepared.
The evaluation of catalyst
By the evaluation method of case study on implementation 1, catalyst is as shown in Figure 1 in the catalytic performance curve graph of different temperature points.
The preparation of embodiment 5 10%Ni/MCM-41-TPAOH (1/5) catalyst
Compared with Example 1, only surfactant TPAOH additive amounts are different, n (TPAOH):N (Ni)=1:5, be
0.5515g, other operating process are same as Example 1, and 10%Ni/MCM-41-TPAOH (1/5) catalyst is prepared.
The evaluation of catalyst
By the evaluation method of case study on implementation 1, catalyst is as shown in Figure 1 in the catalytic performance curve graph of different temperature points.
Experimental data in Fig. 1 shows：The addition of TPAOH make catalyst activity and yield with reaction temperature raising
The trend gradually increased is all presented.Compared with unmodified 10%Ni/MCM-41-TPAOH (0), the additive amount of TPAOH is smaller
When, it is reactive to nickel-base catalyst such as 10%Ni/MCM-41-TPAOH (1/100) and 10%Ni/MCM-41-TPAOH (1/75)
It can increase, but not significantly.It is gradually increased with the additive amount of TPAOH, the activity of catalyst is significantly improved.But
When the increase of TPAOH contents to a certain extent, such as 10%Ni/MCM-41-TPAOH (1/50), the increase width of catalyst reaction performance
Spend not notable, the CO of 10%Ni/MCM-41-TPAOH (1/50) and 10%Ni/MCM-41-TPAOH (1/25) catalyst2Conversion
Rate declines instead, other reaction effects are without significant difference.Comparative result is analyzed from figure, it is believed that surfactant-modified 10%
The reformation performance of Ni/MCM-41-TPAOH (1/50) catalyst is best.Compared with 10%Ni/MCM-41-TPAOH (0), 500
DEG C when, CH4Conversion ratio improve 8%, CO2Conversion ratio improve the yield of 11%, CO and improve 7%.At 700 DEG C,
CH4Conversion ratio improve 15%, CO2Conversion ratio improve the yield of 20%, CO and improve 13%.At 800 DEG C, CH4's
Conversion ratio improves 20%, CO2Conversion ratio improve the yield of 17%, CO and improve 14%.Therefore the present invention obtains most
Excellent surface-active additive amount is n (TPAOH):N (Ni)=1:50.
The preparation of comparative example 6 10%Ni/MCM-41-TPAOH (0) catalyst
By 0.9858gNi (NO3)2·6H2Stirring and dissolving in 30ml distilled water is added in O, and it is molecular sieve supported that 1.8gMCM-41 is added
Body；After room temperature immersion 45min, by above-mentioned mixed serum, water bath method, 110 DEG C of dry 12h are roasted at 550 DEG C at 80 DEG C
4h is obtained without surfactant-modified 10%Ni/MCM-41-TPAOH (0) catalyst.
The evaluation of catalyst
By the evaluation method of case study on implementation 1, catalyst is as shown in Figure 1 in the catalytic performance curve graph of different temperature points.
XRD characterization
It can be seen that 10%Ni/MCM-41-TPAOH (1/50) is compared with 10%Ni/MCM-41-TPAOH (0) in Fig. 2, add
Add it is surfactant-modified after, there is significantly broadened phenomenon in the diffraction maximum of the active component Ni of catalyst, and peak intensity significantly reduces,
Illustrate to make the dispersion degree of active component Ni in catalyst improve using the modification of surfactant tetrapropylammonium hydroxide, grain size becomes
It is small.
TPR table is levied
According to the literature, the reduction peak of low temperature corresponds to active component and carrier and acts on going back for weaker table phase NiO
It is former；High temperature reduction peak belongs to the reduction of the body phase nickel species of active component and carrier strong interaction.As can be seen from Figure 3 four
Either low-temperature reduction peak or high temperature reduction peak is all moved to high-temperature area after the addition of propyl ammonium hydroxide, therefore is shown
The addition of tetrapropylammonium hydroxide enhances the interaction between active component Ni and carrier MCM-41, thus can inhibit activity
In the migration and reunion of carrier surface, this is all advantageous component for improving the catalytic activity of catalyst.
BET is characterized
Fig. 4 can be seen that the Lang Gemiao of 10%Ni/MCM-41-TPAOH (0) and 10%Ni/MCM-41-TPAOH (1/50)
Your curve is all IV types, illustrates that catalyst has good meso-hole structure.The specific surface area of carrier MCM-41 is 1044m2/ g, hole
Diameter is 3.95nm, Kong Rongwei 1.03cm3/g.The specific surface area of 10%Ni/MCM-41-TPAOH (0) catalyst is 684m2/ g, hole
Diameter is 3.69nm, Kong Rongwei 0.63cm3/g.The specific surface area of 10%Ni/MCM-41-TPAOH (1/50) is 883m2/ g, aperture are
3.59nm, Kong Rongwei 0.79cm3/g.Compared with carrier MCM-41,10%Ni/MCM-41-TPAOH (0) and 10%Ni/MCM-
The specific surface area of 41-TPAOH (1/50) is declined, and is the part due to occupying carrier after infusion process load active component Ni
Specific surface area.But the specific surface area of 10%Ni/MCM-41-TPAOH (1/50) is big compared with 10%Ni/MCM-41-TPAOH's (0), this
It is beneficial to dispersions of the active component Ni in catalyst surface, and increases reactant and the contact probability of active sites, to improve
The reactivity of catalyst.
Claims (7)
1. a kind of surfactant enhances CO2The preparation method of reforming catalyst, which is characterized in that this method includes following step
Suddenly：
A, by n (TPAOH):N (Ni)=1:100-1:5 surfactant tetrapropylammonium hydroxide (TPAOH) is dissolved in quantitative steaming
In distilled water, stirring obtains surfactant solution until being completely dissolved；
B, by the Ni (NO of metering3)2·6H2O (with the gross mass of carrier and active component Ni for 100%, activearm in catalyst
It is 10%) to be added in the surfactant solution that a steps obtain to divide the mass percent of Ni, and stirring obtains until being completely dissolved
Mixed solution；
C, in the mixed solution for obtaining the MCM-41 molecular sieves of metering addition b step, dipping obtains mixed serum；
D, the mixed serum that step c obtains is placed in water-bath, water bath method obtains dried powder；
E, the dried powder that Step d obtains is put in an oven, it is dry, obtain catalyst runic；
F, the catalyst runic that step e obtains is placed in Muffle furnace, is roasted to get surfactant-modified 10%Ni/MCM-
41-TPAOH (1/x) catalyst (wherein 1/x indicates the molar ratio of above-mentioned TPAOH and Ni).
2. according to claim 1, enhance CO for surfactant2The preparation method of reforming catalyst, feature exist
In the surfactant is tetrapropylammonium hydroxide (TPAOH).
3. enhancing CO according to surfactant is used for described in claims any one of 1-22The preparation method of reforming catalyst,
It is characterized in that, the additive amount of the surfactant is n (TPAOH):N (Ni)=1:50-1:5.
4. enhancing CO according to surfactant is used for described in claims 32The preparation method of reforming catalyst, which is characterized in that
The additive amount of the surfactant is n (TPAOH):N (Ni)=1:50.
5. enhancing CO for surfactant according to claims 1-4 any one of them2The preparation method of reforming catalyst,
It is characterized in that, the carrier is MCM-41 molecular sieves.
6. enhancing CO according to surfactant is used for described in claims 1-5 any one of them2The preparation side of reforming catalyst
Method, which is characterized in that with the gross mass of carrier and active component Ni for 100%, the quality percentage of active component Ni in catalyst
Than being 10%.
7. claims 1-6 any one of them enhances CO for surfactant2Reforming catalyst is in CO2/CH4It reforms anti-
Application in answering.
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