CN104368345A - Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst - Google Patents

Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst Download PDF

Info

Publication number
CN104368345A
CN104368345A CN201410670739.3A CN201410670739A CN104368345A CN 104368345 A CN104368345 A CN 104368345A CN 201410670739 A CN201410670739 A CN 201410670739A CN 104368345 A CN104368345 A CN 104368345A
Authority
CN
China
Prior art keywords
type high
catalyst
alloy catalyst
preparation
support type
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.)
Pending
Application number
CN201410670739.3A
Other languages
Chinese (zh)
Inventor
张法智
项建峰
闻鑫
杨志祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201410670739.3A priority Critical patent/CN104368345A/en
Publication of CN104368345A publication Critical patent/CN104368345A/en
Priority to PCT/CN2015/074238 priority patent/WO2016078261A1/en
Pending legal-status Critical Current

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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof

Abstract

The invention discloses a preparation method and a catalytic application of a supported type high-dispersion nickel-based alloy catalyst. The preparation method comprises the following steps: by virtue of an in-situ growth method, supporting Ni, M (M=Co, Zn, Cu, Fe, Cr and the like) metal in the form of hydrotalcite on the surface of a microsphere-form gamma-Al2O3 carrier with grain size of 20-40 meshes and in a duct of the microsphere-form gamma-Al2O3 carrier, namely growing lamellar precursor LDHs containing Ni and M metal ions outside and inside a Al2O3 particle to form supported type high-dispersion distribution, converting the lamellar precursor LDHs into a corresponding composite metal oxide by drying and roasting at high temperature, and reducing the composite metal oxide to obtain the supported type high-dispersion nickel-based alloy catalyst with NiM distributed on the outer surface and in the duct of the carrier particle. The supported type high-dispersion nickel-based alloy catalyst is applied to first selective hydrogenation reaction of cracked gasoline, so that the conversion rate, the selectivity and the stability of the catalyst can be effectively improved; and moreover, the supported type high-dispersion nickel-based alloy catalyst can be used for methane reforming, and catalyzing reaction of preparing low-carbon hydrocarbon and alcohol by virtue of CO and CO2 hydrogenation.

Description

A kind of preparation method of support type high-dispersed nickel alloy catalyst and catalytic applications thereof
Technical field
The invention belongs to catalyst preparation technical field, particularly a kind of to utilize in situ synthesis to prepare be the support type high-dispersed nickel alloy catalyst of carrier and the application in drippolene one section of selec-tive hydrogenation field thereof with aluminium oxide.
Background technology
Drippolene is the valuable accessory substance of one of industrial high temperature naphtha thermal cracking ethene and propylene, accounts for 50% ~ 80% of ethylene yield, its C 5 +~ C 12 +hydro carbons is main component, wherein containing a large amount of aromatic hydrocarbons (40 ~ 80%, benzene,toluene,xylene), alkadienes, alkene and alkane, and the therefore high-octane gasoline blending oil of drippolene Chang Zuowei or the raw material of triphen extracting.But its poor stability, needs the styrene of commute formation colloid and carbon distribution and alkadienes to utilize load type metal catalyst to carry out selective hydrogenation at a lower temperature and generates corresponding ethylo benzene and monoene.At present, conventional catalyst is aluminium oxide is the Ni-based of carrier or palladium-based catalyst.Compare palladium-based catalyst, nickel-base catalyst because of its cheap, antitoxin anticol matter is good and to hydro carbons be applicable to hydrogenation/hydrogenolysis performance and be subject to extensive concern.In selective hydrogenation of cracked gasoline reaction, the catalytic performance of nickel-base catalyst utilizes interpolation auxiliary agent usually, modified catalyst carrier and introduce the modes such as novel prevulcanized process and improve.In the middle of these methods, load type bimetal catalyst has been proved to be and effectively can have improved catalytic performance relative to single-metal reforming catalyst.Bimetallic catalyst can show excellent physics and chemical property in conjunction with confinement effect and alloy effect.Especially, bimetallic catalyst can easily by regulating component composition and atomic arrangement to carry out its catalytic performance of modulation.
LDHs is the compound formed by interlayer anion and positively charged laminate ordered fabrication, and its chemical composition general formula is generally as follows: [M 2+ 1-xm 3+ x(OH) 2] x+[A n-] x/nyH 2o, wherein M 2+and M 3+be respectively divalence and trivalent metal cation, be positioned on main body laminate; A n-for interlayer anion; X is M 3+/ (M 2++ M 3+) molar ratio; Y is the number of intermediary water molecule.Form the design feature such as the adjustable sex change in space, the adjustable sex change of host-guest interaction in adjustable sex change, main body laminate charge density and the adjustable sex change that distributes thereof, intercalant anion guest species and the adjustable sex change of quantity, layer because LDHs has body layer sheetmetal ion, such that LDHs is our Development of Novel catalyst, the catalyst carrier of catalyst precarsor and adjustable structure changes and character provides platform highly significant.
Summary of the invention
The object of this invention is to provide a kind of simple preparation support type high-dispersed nickel alloy catalyst method and by this catalyst application in drippolene one section of selec-tive hydrogenation.
The present invention by situ synthesis by Ni, M (M=Co, Zn, Cu, Fe, Cr etc.) metal with the form load of houghite at particle diameter for 20-40 object microspheroidal γ-Al 2o 3in carrier surface and duct thereof, namely at Al 2o 3extra-granular and growth inside contain the stratiform presoma LDHs of Ni, M metal ion, form the distribution of support type high dispersive, drying, under high temperature, roasting changes corresponding composite metal oxide into, obtain NiM after reduction and be distributed in support type high-dispersed nickel alloy catalyst in carrier particle exterior surface and duct, be applied to, in drippolene one section of selective hydrogenation reaction, effectively to improve the conversion ratio of catalyst, selective and stability, also can be used for methane reforming and catalysis CO, CO 2hydrogenation is for the reaction of lower carbon number hydrocarbons and alcohol.
Support type high-dispersed nickel alloy catalyst of the present invention, its composition structure is: alloy NiM is distributed in γ-Al 2o 3in carrier particle exterior surface and duct thereof, form the distribution of support type high dispersive alloy; Alloy NiM particle diameter is at 1-8nm, γ-Al 2o 3diameter of carrier is 20-40 order; With catalyst gross mass for benchmark, alloy NiM total load amount is 6-12wt%; M is Co, Zn, Cu, Fe or Cr.
The concrete preparation method of support type high-dispersed nickel alloy catalyst of the present invention is as follows:
A. be 20-40 object γ-Al by 3-5g particle diameter 2o 3particle, soluble nickel salt, soluble M salt, urea, join in 10ml deionized water fast, transfer to after vacuum impregnation 1-3h in autoclave, crystallization 12-24h at 90-130 DEG C of temperature, filter, spend deionized water particle, obtain support type high dispersive NiMAl-LDHs/Al 2o 3precursor;
B. by NiMAl-LDHs/Al 2o 3precursor is dry 6-12h at 60-100 DEG C, and then 400-600 DEG C of roasting 2-8h, obtains LP-NiMO/Al 2o 3;
C. the LP-NiMO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 400-600 DEG C of heat treatment 0.5-2h, heating rate is 5-10 DEG C/min; Finally flow velocity is adopted to be the H of 30-80mL/min 2be the N of 10-30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 400-600 DEG C, and the recovery time is 2-5h, and reduction pressure is 0.5-1MPa, namely obtains support type high-dispersed nickel alloy catalyst after completing.
In described steps A, the mol ratio of urea and metal ion is (2:1)-(4:1).
Described soluble nickel salt is nickel nitrate, nickel chloride or nickelous sulfate.
Described soluble M salt is nitric acid M, chlorination M or sulfuric acid M.
The support type high-dispersed nickel alloy catalyst above-mentioned method prepared is applied to catalytic cracking gasoline one section of selective hydrogenation reaction, its process conditions are: reaction temperature is 40-60 DEG C, the volume ratio of hydrogen and drippolene is 50-100, mass space velocity WHSV=10-30h -1, catalyst amount is 1.0-1.5g, and reaction gross pressure is 2.0-3.5MPa, and hydrogen partial pressure is 0.4-3.0MPa, reaction time 12-120h.
The support type high-dispersed nickel alloy catalyst that the present invention adopts in situ synthesis to prepare, Al 2o 3ball is not only used as catalyst carrier but also is used as the Al of growth in situ synthesis NiAl-LDHs presoma 3+source, obtains NiM/Al by NiMAl-LDHs presoma 2o 3alloy catalyst, this catalyst not only increases cinnamic conversion ratio, and can improve the selective of ethylo benzene, and then improves selective hydrogenation of cracked gasoline performance.And catalyst preparation process is without the need to an organic solvent or additive, and method is easy, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is embodiment 12Ni1CoAl-LDHs/Al 2o 3(a, b) and LP-2Ni1CoO/Al 2o 3the surperficial SEM photo (a, c) of (c, d) and tangent plane SEM photo (b, d) and LP-2Ni1Co/Al 2o 3details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope figure and line sweep figure (e) of corresponding metallic particles.
Fig. 2 is γ-Al in embodiment 1 2o 3carrier (a), NiAl-LDHs/Al 2o 3(b) presoma, and Ni:Co mass fraction is than the mNinCoAl-LDHs/Al for 3:1 (c), 2:1 (d), 1:1 (e) 2o 3presoma and CoAl-LDHs/Al 2o 3the XRD figure of presoma (f).
Fig. 3 is LP-Ni/Al in embodiment 1 2o 3(a, b), LP-2Ni1Co/Al 2o 3(c, d), LP-1Ni1Co/Al 2o 3(e, f) and IM-2Ni1Co/Al 2o 3the photo of the high-resolution-ration transmission electric-lens of (g, h).Particle size distribution (calculates based on each sample 150 particles) as shown in the figure.
Fig. 4 is support type high-dispersed nickel alloy catalyst in embodiment 1, LP-Ni/Al 2o 3catalyst, LP-Co/Al 2o 3catalyst and IM-NiCo/Al 2o 3catalyst is to the curve of styrene conversion rate-time.
Fig. 5 is LP-2Ni1Co/Al in embodiment 1 2o 3catalyst is to the curve of styrene conversion rate and the study on the stability of selective-time.
Detailed description of the invention
Embodiment 1
A. be 20-40 object γ-Al by 5g particle diameter 2o 3particle, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, urea, join in 10ml deionized water fast, Ni and Co gross mass mark is 12wt%, different Ni/Co mass fraction ratio (m/n=3/1,2/1,1/1), urea: (Ni 2++ Co 2+) amount of substance ratio be 2:1, transfer to after vacuum impregnation 1h in autoclave, crystallization 24h at 130 DEG C of temperature, filter, spending deionized water particle to PH is 7, obtains support type high dispersive NiCoAl-LDHs/Al 2o 3precursor (SEM figure and XRD spectra are shown in Fig. 1 and Fig. 2);
B. by NiCoAl-LDHs/Al 2o 3precursor is dry 10h at 70 DEG C, and then 450 DEG C of roasting 4h, obtain LP-NiCoO/Al 2o 3;
C. the LP-NiCoO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 500 DEG C of heat treatment 0.5h, heating rate is 10 DEG C/min; Finally flow velocity is adopted to be the H of 50mL/min 2be the N of 30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 500 DEG C, and the recovery time is 3h, and reduction pressure is 0.5MPa, namely obtains support type high-dispersed nickel alloy catalyst, be designated as LP-NiCo/Al after completing 2o 3.
By the process conditions that the support type high-dispersed nickel alloy catalyst of above-mentioned preparation is used for drippolene one section of selective hydrogenation reaction be: catalyst amount 1.1g, reaction temperature is 40-60 DEG C, and the volume ratio of hydrogen and drippolene is 80, mass space velocity WHSV=30h -1, reaction gross pressure is 3.0MPa, and hydrogen partial pressure is 0.4-3.0MPa, reaction time 12h.The drippolene analogies composition used is styrene 10wt%, toluene 35wt% and normal heptane 55wt%, and product is analyzed by gas-chromatography.
Active component ratio and reaction time two conditions are investigated styrene conversion rate, the loaded catalyst prepared with traditional infusion process sample in contrast.Reaction condition is as follows, styrene conversion rate with the change of each condition as shown in Fig. 4 Fig. 5:
A) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 12.0wt%, Co load capacity is 0 (not adding Co salt), reaction time: 12h.(Fig. 4)
B) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 9.0wt%, Co load capacity is 3.0wt%, reaction time: 12h.(Fig. 4)
C) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 8.0wt%, Co load capacity is 4.0wt%, reaction time: 12h.(Fig. 4)
D) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 6.0wt%, Co load capacity is 6.0wt%, reaction time: 12h.(Fig. 4)
E) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 0, Co load capacity is 12.0wt% (not adding Ni salt), reaction time: 12h.(Fig. 4)
F) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 8.0wt%, Co load capacity is 4.0wt% (traditional infusion process preparation), reaction time: 12h.(Fig. 4)
G) reaction temperature: 60 DEG C, hydrogen partial pressure: 2.0MPa, Ni load capacity is 8.0wt%, Co load capacity is 4.0wt%, reaction time: 117h.(Fig. 5)
Carry out SEM and XRD to the material obtained to characterize, the results are shown in Figure 1 and Fig. 2, the 2Ni1CoAl-LDHs/Al obtained as seen from the figure 2o 3surface and tangent plane all grow NiCoAl-LDHs, reticulate and are uniformly distributed.
HRETEM sign is carried out to the material obtained, the results are shown in Figure 3, the LP-2Ni1Co/Al obtained as seen from Figure 3 2o 3in particle, 1-4nm particle size has accounted for 63%, LP-Ni/Al 2o 353%, and impregnated sample IM-2Ni1Co/Al 2o 3in be greater than 16nm particle and accounted for 53%.(LP refers to the preparation of growth in situ method, after described IM refer to typical impregnation method preparation)
STEM sign is carried out to the material obtained, the results are shown in Figure 1 (e), the LP-2Ni1Co/Al obtained can be found out by Fig. 1 (e) 2o 3define NiCo alloy phase.
Support type high-dispersed nickel alloy catalyst provided by the invention, is particularly suitable for drippolene one section of selective hydrogenation reaction.The IM-2Ni1Co/Al prepared with traditional infusion process 2o 3catalyst and monometallic LP-Ni/Al 2o 3catalyst is compared, and result is as shown in Fig. 4 Fig. 5:
1) as can be seen from Figure 4, cinnamic conversion ratio reaches peak 100.0% along with adding of Co, continues to add Co to LP-1Ni1Co/Al 2o 3, conversion ratio has dropped to 88.7%, and LP-Co/Al 2o 3but 10.6% is only had.Known appropriate Co can improve catalyst hydrogenation performance.
2) as can be seen from Figure 4, compared with the catalyst prepared with in situ synthesis, catalyst I M-2Ni1Co/Al prepared by traditional infusion process 2o 3conversion ratio only has 69.7%, and this illustrates that catalyst prepared by situ synthesis has excellent Activity and stabill, is not only that it has confinement effect, and the alloy phase of formation more has excellent cooperative effect.Confinement effect shows as active component and carrier has strong interaction, and the active component particles of formation is also little, and the Heterosis that particle size is little is the formation that can suppress carbon distribution.And the alloy phase formed more can improve the selectivity of catalyst and also can suppress the formation of carbon distribution.
3) as can be seen from Figure 4, the alloy catalyst prepared of in situ synthesis is relative to LP-Ni/Al 2o 3, conversion ratio and selective all apparently higher than single-metal reforming catalyst, the alloy effect that known alloy catalyst has and high activity, high selectivity and high stability that cooperative effect is brought.
4) as can be seen from Figure 5, LP-2Ni1Co/Al 2o 3initial activity reach 100.0%, react and can remain on 93.2% after 117 hours, selectively remain on 100.0%, carbon distribution value also only only has 2.76wt%, and is 1.65wt% in reaction after 12 hours.But for LP-Ni/Al 2o 3react and just reach 2.43wt%, IM-2Ni1Co/Al in 12 hours 2o 3reach 2.57wt% especially, known LP-2Ni1Co/Al 2o 3there is excellent anti-carbon performance.
Embodiment 2
A. be 20-40 object γ-Al by 5g particle diameter 2o 3particle, Ni (NO 3) 26H 2o, Zn (NO 3) 26H 2o, urea, join in 10ml deionized water fast, Ni and Zn gross mass mark is 12wt%, different Ni/Zn mass fraction ratio (m/n=3/1,2/1,1/1), urea: (Ni 2++ Zn 2+) amount of substance ratio be 2:1, transfer to after vacuum impregnation 1h in autoclave, crystallization 24h at 130 DEG C of temperature, filter, spending deionized water particle to PH is 7, obtains support type high dispersive NiZnAl-LDHs/Al 2o 3precursor;
B. by NiZnAl-LDHs/Al 2o 3precursor is dry 10h at 70 DEG C, and then 450 DEG C of roasting 4h, obtain LP-NiZnO/Al 2o 3;
C. the LP-NiZnO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 500 DEG C of heat treatment 0.5h, heating rate is 10 DEG C/min; Finally flow velocity is adopted to be the H of 50mL/min 2be the N of 30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 500 DEG C, and the recovery time is 3h, and reduction pressure is 0.5MPa, namely obtains support type high-dispersed nickel alloy catalyst, be designated as LP-NiZn/Al after completing 2o 3.
Embodiment 3
A. be 20-40 object γ-Al by 5g particle diameter 2o 3particle, Ni (NO 3) 26H 2o, Cu (NO 3) 23H 2o, urea, join in 10ml deionized water fast, Ni and Cu gross mass mark is 12wt%, different Ni/Cu mass fraction ratio (m/n=3/1,2/1,1/1), urea: (Ni 2++ Cu 2+) amount of substance ratio be 2:1, transfer to after vacuum impregnation 1h in autoclave, crystallization 24h at 130 DEG C of temperature, filter, spending deionized water particle to PH is 7, obtains support type high dispersive NiCuAl-LDHs/Al 2o 3precursor;
B. by NiCuAl-LDHs/Al 2o 3precursor is dry 10h at 70 DEG C, and then 450 DEG C of roasting 4h, obtain LP-NiCuO/Al 2o 3;
C. the LP-NiCuO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 500 DEG C of heat treatment 0.5h, heating rate is 10 DEG C/min; Finally flow velocity is adopted to be the H of 50mL/min 2be the N of 30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 500 DEG C, and the recovery time is 3h, and reduction pressure is 0.5MPa, namely obtains support type high-dispersed nickel alloy catalyst, be designated as LP-NiCu/Al after completing 2o 3.
Embodiment 4
A. be 20-40 object γ-Al by 5g particle diameter 2o 3particle, Ni (NO 3) 26H 2o, Fe (NO 3) 39H 2o, urea, join in 10ml deionized water fast, Ni and Fe gross mass mark is 12wt%, different Ni/Fe mass fraction ratio (m/n=3/1,2/1,1/1), urea: (Ni 2++ Fe 3+) amount of substance ratio be 2:1, transfer to after vacuum impregnation 1h in autoclave, crystallization 24h at 130 DEG C of temperature, filter, spending deionized water particle to PH is 7, obtains support type high dispersive NiFeAl-LDHs/Al 2o 3precursor;
B. by NiFeAl-LDHs/Al 2o 3precursor is dry 10h at 70 DEG C, and then 450 DEG C of roasting 4h, obtain LP-NiFeO/Al 2o 3;
C. the LP-NiFeO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 500 DEG C of heat treatment 0.5h, heating rate is 10 DEG C/min; Finally flow velocity is adopted to be the H of 50mL/min 2be the N of 30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 500 DEG C, and the recovery time is 3h, and reduction pressure is 0.5MPa, namely obtains support type high-dispersed nickel alloy catalyst, be designated as LP-NiFe/Al after completing 2o 3.
Embodiment 5
A. be 20-40 object γ-Al by 5g particle diameter 2o 3particle, Ni (NO 3) 26H 2o, Cr (NO 3) 39H 2o, urea, join in 10ml deionized water fast, Ni and Cr gross mass mark is 12wt%, different Ni/Cr mass fraction ratio (m/n=3/1,2/1,1/1), urea: (Ni 2++ Zn 2+) amount of substance ratio be 2:1, transfer to after vacuum impregnation 1 in autoclave, crystallization 24h at 130 DEG C of temperature, filter, spending deionized water particle to PH is 7, obtains support type high dispersive NiCrAl-LDHs/Al 2o 3precursor;
B. by NiCrAl-LDHs/Al 2o 3precursor is dry 10h at 70 DEG C, and then 450 DEG C of roasting 4h, obtain LP-NiCrO/Al 2o 3;
C. the LP-NiCrO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 500 DEG C of heat treatment 0.5h, heating rate is 10 DEG C/min; Finally flow velocity is adopted to be the H of 50mL/min 2be the N of 30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 500 DEG C, and the recovery time is 3h, and reduction pressure is 0.5MPa, namely obtains support type high-dispersed nickel alloy catalyst, be designated as LP-NiCr/Al after completing 2o 3.

Claims (7)

1. a support type high-dispersed nickel alloy catalyst, is characterized in that, its composition structure is: alloy NiM is distributed in γ-Al 2o 3in carrier particle exterior surface and duct thereof, form the distribution of support type high dispersive alloy; Alloy NiM particle diameter is at 1-8nm, γ-Al 2o 3diameter of carrier is 20-40 order; With catalyst gross mass for benchmark, alloy NiM total load amount is 6-12wt%; M is Co, Zn, Cu, Fe or Cr.
2. the preparation method of support type high-dispersed nickel alloy catalyst according to claim 1, it is characterized in that, its concrete operation step is as follows:
A. be 20-40 object γ-Al by 3-5g particle diameter 2o 3particle, soluble nickel salt, soluble M salt, urea, join in 10ml deionized water fast, transfer to after vacuum impregnation 1-3h in autoclave, crystallization 12-24h at 90-130 DEG C of temperature, filter, spend deionized water particle, obtain support type high dispersive NiMAl-LDHs/Al 2o 3precursor;
B. by NiMAl-LDHs/Al 2o 3precursor is dry 6-12h at 60-100 DEG C, and then 400-600 DEG C of roasting 2-8h, obtains LP-NiMO/Al 2o 3;
C. the LP-NiMO/Al prepared by step B 2o 3load in micro fixed-bed reactor, at N 2protect lower 400-600 DEG C of heat treatment 0.5-2h, heating rate is 5-10 DEG C/min; Finally flow velocity is adopted to be the H of 30-80mL/min 2be the N of 10-30mL/min with flow velocity 2gaseous mixture reduce, reduction temperature is 400-600 DEG C, and the recovery time is 2-5h, and reduction pressure is 0.5-1MPa, namely obtains support type high-dispersed nickel alloy catalyst after completing.
3. preparation method according to claim 2, is characterized in that, in described steps A, the mol ratio of urea and metal ion is (2:1)-(4:1).
4. preparation method according to claim 2, is characterized in that, described soluble nickel salt is nickel nitrate, nickel chloride or nickelous sulfate.
5. preparation method according to claim 2, is characterized in that, described soluble M salt is nitric acid M, chlorination M or sulfuric acid M.
6. the application of support type high-dispersed nickel alloy catalyst catalytic cracking gasoline one section of selective hydrogenation reaction for preparing of method according to claim 2.
7. application according to claim 6, is characterized in that, the process conditions of described catalytic cracking gasoline one section of selective hydrogenation reaction are: reaction temperature is 40-60 DEG C, and the volume ratio of hydrogen and drippolene is 50-100, mass space velocity WHSV=10-30h -1, catalyst amount is 1.0-1.5g, and reaction gross pressure is 2.0-3.5MPa, and hydrogen partial pressure is 0.4-3.0MPa, reaction time 12-120h.
CN201410670739.3A 2014-11-20 2014-11-20 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst Pending CN104368345A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201410670739.3A CN104368345A (en) 2014-11-20 2014-11-20 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst
PCT/CN2015/074238 WO2016078261A1 (en) 2014-11-20 2015-03-13 Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410670739.3A CN104368345A (en) 2014-11-20 2014-11-20 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst

Publications (1)

Publication Number Publication Date
CN104368345A true CN104368345A (en) 2015-02-25

Family

ID=52547691

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410670739.3A Pending CN104368345A (en) 2014-11-20 2014-11-20 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst

Country Status (2)

Country Link
CN (1) CN104368345A (en)
WO (1) WO2016078261A1 (en)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016078261A1 (en) * 2014-11-20 2016-05-26 北京化工大学 Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof
CN106040243A (en) * 2016-05-30 2016-10-26 中国科学院福建物质结构研究所 Catalyst for preparing synthetic gas by reforming methane and carbon dioxide and preparation method thereof
CN106311281A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst for synthesis of low carbon alcohol by hydrogenation of carbon dioxide as well as preparation method and application thereof
CN106423199A (en) * 2016-09-06 2017-02-22 北京化工大学 Preparation method and catalytic application of supported high-dispersity NiRu bimetallic catalyst
CN107537504A (en) * 2016-06-29 2018-01-05 华东师范大学 A kind of self-supporting Raney nickel and its preparation and application
CN107790133A (en) * 2017-11-07 2018-03-13 中国科学院理化技术研究所 A kind of ferro-cobalt based photocatalyst and its preparation and application
CN107876059A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of nickel zinc bimetallic catalyst and its preparation method and application
JPWO2017010491A1 (en) * 2015-07-15 2018-04-26 古河電気工業株式会社 Nanocrystal composite catalyst for hydrogen storage and supply, nanocrystal composite catalyst mixture for hydrogen storage and supply, and hydrogen supply method
CN108380218A (en) * 2018-03-16 2018-08-10 福州大学 A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof
CN106000410B (en) * 2016-05-23 2018-09-21 北京化工大学 A kind of stable dispersion Co base catalyst of synthesis gas ethyl alcohol and higher alcohol
CN108636414A (en) * 2018-05-23 2018-10-12 广东工业大学 A kind of preparation method and applications of composition, bimetallic catalyst
CN108777309A (en) * 2018-05-15 2018-11-09 北京化工大学 A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications
CN109201065A (en) * 2018-09-27 2019-01-15 苏州大学 A kind of nickel foam composite material and preparation method and the application in photoelectrocatalysis removal water pollutant
WO2019015528A1 (en) * 2017-07-19 2019-01-24 武汉丰盈长江生态科技研究总院有限公司 Nickel-based reforming catalyst for circulating fluidized bed, preparation method therefor, and application thereof
CN105879876B (en) * 2016-05-09 2019-03-05 太原理工大学 The preparation method of nickel-base catalyst for methane and carbon dioxide preparing synthetic gas by reforming
CN109550500A (en) * 2018-12-11 2019-04-02 常州大学 It is a kind of can Magnetic Isolation graphene-based zinc-iron mixing bimetallic oxide photochemical catalyst preparation method and applications
CN109569612A (en) * 2018-12-25 2019-04-05 哈尔滨工业大学 It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof
CN109772332A (en) * 2017-11-15 2019-05-21 中国科学院大连化学物理研究所 A kind of load type metal catalyst directly prepared by solid and its application
CN110465295A (en) * 2018-05-10 2019-11-19 李大鹏 A kind of floating bed hydrogenation multiple elements design ferrum-based catalyst and preparation method thereof
CN110652972A (en) * 2019-09-03 2020-01-07 北京化工大学 Hydrotalcite inorganic-organic composite fiber membrane and preparation method thereof
CN110813296A (en) * 2019-10-08 2020-02-21 中国科学院兰州化学物理研究所 Preparation method of nano-porous Ni-Fe alloy catalyst
US10682608B2 (en) 2015-07-15 2020-06-16 Furukawa Electric Co., Ltd. Base material-integrated nanocrystalline metal oxide composite-containing catalyst, method for manufacturing the same, and catalyst component
CN111495378A (en) * 2020-05-28 2020-08-07 中建材蚌埠玻璃工业设计研究院有限公司 Methanation catalyst and preparation method thereof
CN111659402A (en) * 2020-05-21 2020-09-15 中国科学院广州能源研究所 CO (carbon monoxide)2Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof
CN112264110A (en) * 2020-10-26 2021-01-26 深圳市合众清洁能源研究院 Supported nickel metal catalyst for hydrogen production and preparation method and application thereof
CN112316949A (en) * 2020-11-05 2021-02-05 山东中科新材料研究院有限公司 Preparation method and use method of carbon-containing supported nickel alloy catalyst
CN114308087A (en) * 2022-01-13 2022-04-12 福州大学 Supported nickel phosphide catalyst for petroleum resin hydrogenation and preparation method thereof

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110893346A (en) * 2018-09-12 2020-03-20 华东理工大学 Bimetallic low-temperature methanation catalyst and preparation method and application thereof
CN109794255B (en) * 2019-02-01 2022-05-10 广东工业大学 Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol
CN110975855B (en) * 2019-12-18 2023-05-30 浙江工业大学 Catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro-chloromethane, preparation method and application thereof
CN111330594A (en) * 2020-03-31 2020-06-26 中国工程物理研究院材料研究所 Preparation method and application of hydrophobic layered double-metal oxide catalyst
CN113713817B (en) * 2020-05-26 2023-06-27 中国科学院大连化学物理研究所 Method for preparing n-propanol by catalyzing propanal hydrogenation by nickel-based catalyst
CN114433094B (en) * 2020-10-20 2024-01-09 中国石油化工股份有限公司 Nickel catalyst and preparation method and application thereof
CN114471571B (en) * 2020-10-26 2023-10-13 中国石油化工股份有限公司 Catalyst for preparing isooctyl aldehyde by hydrogenation of isooctyl aldehyde, preparation method and application
CN112403466B (en) * 2020-11-06 2023-01-03 上海簇睿低碳能源技术有限公司 Preparation method of core-shell catalyst for dry reforming of methane and carbon dioxide
CN112657482B (en) * 2020-11-24 2023-06-13 大连理工大学 Solid acid catalyst and propylene oligomer obtained by using same
CN112542328B (en) * 2020-12-02 2022-07-05 浙江大学 Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof
CN113731443B (en) * 2021-09-22 2023-08-01 西北工业大学 Pt/CoFe-LDH supported nano solid catalyst and preparation method and application thereof
CN113663714B (en) * 2021-09-23 2023-08-22 中国科学院上海高等研究院 Aluminum nitride-based catalyst and preparation method and application thereof
CN114011418A (en) * 2021-12-06 2022-02-08 无锡碳谷科技有限公司 Preparation method of methane cracking catalyst
CN114471576B (en) * 2021-12-28 2022-12-27 南京工业大学 CuMgAl @ gamma-Al 2 O 3 Solid catalyst and application thereof
CN115475661B (en) * 2022-10-18 2023-09-08 理工清科(重庆)先进材料研究院有限公司 Reduce MgH 2 Ni-loaded MOF catalyst with hydrogen release activation energy and preparation method and application thereof
CN116328775A (en) * 2023-01-05 2023-06-27 大连理工大学 Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester
CN116351429A (en) * 2023-03-24 2023-06-30 中原工学院 Self-supporting nickel-gallium alloy catalyst and preparation method and application thereof
CN116139865A (en) * 2023-04-04 2023-05-23 厦门大学 Supported FeNi bimetallic catalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102247865A (en) * 2010-05-21 2011-11-23 中国石油化工股份有限公司 Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof
US20120046160A1 (en) * 2010-08-19 2012-02-23 Mark Crocker Conversion of triglycerides to hydrocarbons by means of a mixed oxide catalyst
CN102380374A (en) * 2010-09-01 2012-03-21 中国石油天然气股份有限公司 Preparation method of palladium group hydrogenation catalyst
CN103223342A (en) * 2013-05-22 2013-07-31 北京化工大学 Preparation method and application of eggshell-type nickel-based catalyst

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6193877B1 (en) * 1996-08-23 2001-02-27 Exxon Research And Engineering Company Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds
CN101822986B (en) * 2010-03-31 2012-05-09 北京化工大学 Preparation method of catalyst capable of controlling growth of carbon nano pipe and carbon fibre
WO2011147090A1 (en) * 2010-05-27 2011-12-01 北京化工大学 Catalyst supporting noble metal and in-suit preparing method thereof
CN104368345A (en) * 2014-11-20 2015-02-25 北京化工大学 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102247865A (en) * 2010-05-21 2011-11-23 中国石油化工股份有限公司 Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof
US20120046160A1 (en) * 2010-08-19 2012-02-23 Mark Crocker Conversion of triglycerides to hydrocarbons by means of a mixed oxide catalyst
CN102380374A (en) * 2010-09-01 2012-03-21 中国石油天然气股份有限公司 Preparation method of palladium group hydrogenation catalyst
CN103223342A (en) * 2013-05-22 2013-07-31 北京化工大学 Preparation method and application of eggshell-type nickel-based catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANFENG XIANG ET AL: ""Supported Nickel-Cobalt Bimetallic Catalysts Derived from Layered Double Hydroxide Precursors for Selective Hydrogenation of Pyrolysis Gasoline"", 《INDUSTRIAL ＆ ENGINEERING CHEMISTRY RESEARCH》 *

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016078261A1 (en) * 2014-11-20 2016-05-26 北京化工大学 Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof
CN106311281A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst for synthesis of low carbon alcohol by hydrogenation of carbon dioxide as well as preparation method and application thereof
CN106311281B (en) * 2015-07-02 2019-03-19 中国科学院大连化学物理研究所 Hydrogenation of carbon dioxide formate low-carbon alcohol catalyst and its preparation method and application
US10682608B2 (en) 2015-07-15 2020-06-16 Furukawa Electric Co., Ltd. Base material-integrated nanocrystalline metal oxide composite-containing catalyst, method for manufacturing the same, and catalyst component
US10584030B2 (en) 2015-07-15 2020-03-10 Furukawa Electric Co., Ltd. Nanocrystalline composite catalyst for storing/supplying hydrogen, nanocrystalline composite catalyst mixture for storing/supplying hydrogen, and method for supplying hydrogen
EP3323506A4 (en) * 2015-07-15 2019-05-08 Furukawa Electric Co. Ltd. Nanocrystal complex catalyst for storing/supplying hydrogen, nanocrystal complex catalyst mixture for storing/supplying hydrogen, and method for supplying hydrogen
JPWO2017010491A1 (en) * 2015-07-15 2018-04-26 古河電気工業株式会社 Nanocrystal composite catalyst for hydrogen storage and supply, nanocrystal composite catalyst mixture for hydrogen storage and supply, and hydrogen supply method
CN105879876B (en) * 2016-05-09 2019-03-05 太原理工大学 The preparation method of nickel-base catalyst for methane and carbon dioxide preparing synthetic gas by reforming
CN106000410B (en) * 2016-05-23 2018-09-21 北京化工大学 A kind of stable dispersion Co base catalyst of synthesis gas ethyl alcohol and higher alcohol
CN106040243A (en) * 2016-05-30 2016-10-26 中国科学院福建物质结构研究所 Catalyst for preparing synthetic gas by reforming methane and carbon dioxide and preparation method thereof
CN107537504A (en) * 2016-06-29 2018-01-05 华东师范大学 A kind of self-supporting Raney nickel and its preparation and application
CN106423199A (en) * 2016-09-06 2017-02-22 北京化工大学 Preparation method and catalytic application of supported high-dispersity NiRu bimetallic catalyst
CN107876059A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of nickel zinc bimetallic catalyst and its preparation method and application
WO2019015528A1 (en) * 2017-07-19 2019-01-24 武汉丰盈长江生态科技研究总院有限公司 Nickel-based reforming catalyst for circulating fluidized bed, preparation method therefor, and application thereof
CN107790133B (en) * 2017-11-07 2020-09-18 中国科学院理化技术研究所 Cobalt-iron-based photocatalyst and preparation and application thereof
CN107790133A (en) * 2017-11-07 2018-03-13 中国科学院理化技术研究所 A kind of ferro-cobalt based photocatalyst and its preparation and application
CN109772332A (en) * 2017-11-15 2019-05-21 中国科学院大连化学物理研究所 A kind of load type metal catalyst directly prepared by solid and its application
CN109772332B (en) * 2017-11-15 2022-03-18 中国科学院大连化学物理研究所 Supported metal catalyst directly prepared from solid and application thereof
CN108380218A (en) * 2018-03-16 2018-08-10 福州大学 A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof
CN110465295A (en) * 2018-05-10 2019-11-19 李大鹏 A kind of floating bed hydrogenation multiple elements design ferrum-based catalyst and preparation method thereof
CN110465295B (en) * 2018-05-10 2022-04-19 李大鹏 Suspension bed hydrogenation multi-element composite iron-based catalyst and preparation method thereof
CN108777309A (en) * 2018-05-15 2018-11-09 北京化工大学 A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications
CN108636414A (en) * 2018-05-23 2018-10-12 广东工业大学 A kind of preparation method and applications of composition, bimetallic catalyst
CN109201065A (en) * 2018-09-27 2019-01-15 苏州大学 A kind of nickel foam composite material and preparation method and the application in photoelectrocatalysis removal water pollutant
CN109550500B (en) * 2018-12-11 2021-11-02 常州大学 Preparation method and application of magnetically separable graphene-based zinc-iron mixed bimetallic oxide photocatalyst
CN109550500A (en) * 2018-12-11 2019-04-02 常州大学 It is a kind of can Magnetic Isolation graphene-based zinc-iron mixing bimetallic oxide photochemical catalyst preparation method and applications
CN109569612A (en) * 2018-12-25 2019-04-05 哈尔滨工业大学 It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof
CN109569612B (en) * 2018-12-25 2020-12-11 哈尔滨工业大学 Nano binary metal base tar catalytic cracking catalyst using active semicoke as carrier and preparation method thereof
CN110652972A (en) * 2019-09-03 2020-01-07 北京化工大学 Hydrotalcite inorganic-organic composite fiber membrane and preparation method thereof
CN110813296A (en) * 2019-10-08 2020-02-21 中国科学院兰州化学物理研究所 Preparation method of nano-porous Ni-Fe alloy catalyst
CN111659402A (en) * 2020-05-21 2020-09-15 中国科学院广州能源研究所 CO (carbon monoxide)2Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof
CN111495378A (en) * 2020-05-28 2020-08-07 中建材蚌埠玻璃工业设计研究院有限公司 Methanation catalyst and preparation method thereof
CN111495378B (en) * 2020-05-28 2023-07-21 中建材玻璃新材料研究院集团有限公司 Methanation catalyst and preparation method thereof
CN112264110A (en) * 2020-10-26 2021-01-26 深圳市合众清洁能源研究院 Supported nickel metal catalyst for hydrogen production and preparation method and application thereof
CN112316949A (en) * 2020-11-05 2021-02-05 山东中科新材料研究院有限公司 Preparation method and use method of carbon-containing supported nickel alloy catalyst
CN114308087A (en) * 2022-01-13 2022-04-12 福州大学 Supported nickel phosphide catalyst for petroleum resin hydrogenation and preparation method thereof

Also Published As

Publication number Publication date
WO2016078261A1 (en) 2016-05-26

Similar Documents

Publication Publication Date Title
CN104368345A (en) Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst
CN106031871B (en) A kind of CO2Hydrogenation takes ferrum-based catalyst and its preparation and the application of low-carbon alkene
Nikolaev et al. Catalytic hydrogenation of alkyne and alkadiene impurities from alkenes. Practical and theoretical aspects
Yang et al. Selective synthesis of olefins via CO2 hydrogenation over transition-metal-doped iron-based catalysts
CN106423199A (en) Preparation method and catalytic application of supported high-dispersity NiRu bimetallic catalyst
EP3390281A1 (en) Crystalline transition metal oxy-hydroxide molybdate
CN103223342A (en) Preparation method and application of eggshell-type nickel-based catalyst
CN1325608C (en) Process for preparing olefin by catalytic cracking of hydrocarbon
CN105195169B (en) A kind of catalyst of F- T synthesis preparing low-carbon olefins and preparation method and application
Du et al. Effects of impregnation strategy on structure and performance of bimetallic CoFe/AC catalysts for higher alcohols synthesis from syngas
CN111346672B (en) Method for preparing low-carbon olefin by doping heteroatom molecular sieve to catalyze synthesis gas with high selectivity
EP3023148B1 (en) Method for manufacturing multi-component composite metal oxide catalyst
CN103464193B (en) Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof
CN103131456B (en) A kind of method of being synthesized liquefied petroleum gas (LPG) and BTX aromatics by butanols
CN104098427A (en) C3 fraction selective hydrogenation method
Qu et al. Advances in zeolite-supported metal catalysts for propane dehydrogenation
CN109225249A (en) A kind of nickel manganese aluminium composite oxide catalyst for acetic acid self-heating reforming hydrogen manufacturing
Sun et al. The effect of CeO 2 on the hydrodenitrogenation performance of bulk Ni 2 P
CN113559922A (en) Bimetallic catalyst for preparing cyclohexylbenzene by benzene hydrogenation and preparation method and application thereof
Song et al. Synthesis of an yttrium-modified bulk Ni2P catalyst with high hydrodesulfurization activity
Xu et al. Higher alcohol synthesis from syngas over KCoMoP catalysts
CN105289712A (en) Catalyst for producing propylene by converting through coupling of methanol and C4-hydrocarbons and application of catalyst
CN103920525B (en) A kind of preparation method and application of the catalyst of dimethyl ether and benzene alkylation
CN102861583B (en) Cobalt-based Fischer-Tropasch synthetic catalyst and preparation method
CN105435801B (en) Load typed iron catalyst and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150225