CN108620070A - A kind of catalyst and preparation method thereof for synthesis gas C2 oxygenatedchemicals - Google Patents
A kind of catalyst and preparation method thereof for synthesis gas C2 oxygenatedchemicals Download PDFInfo
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- CN108620070A CN108620070A CN201810330416.8A CN201810330416A CN108620070A CN 108620070 A CN108620070 A CN 108620070A CN 201810330416 A CN201810330416 A CN 201810330416A CN 108620070 A CN108620070 A CN 108620070A
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- oxygenatedchemicals
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910019603 Rh2O3 Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000010948 rhodium Substances 0.000 claims description 47
- 239000011572 manganese Substances 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000020477 pH reduction Effects 0.000 claims description 13
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 230000009514 concussion Effects 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 4
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 19
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 12
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 11
- 239000003643 water by type Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 229910001630 radium chloride Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- -1 propyl alcohols Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of catalyst of synthesis gas C2 oxygenatedchemicals, and the catalyst is with nano-TiO2For carrier, using Rh as active component, using Mn as auxiliary agent；The load capacity of Rh is 0.05 5%, and the load capacity of Mn is 0.5 10%.The invention also discloses the preparation methods of catalyst：Using titanium dioxide as carrier, Rh is made after dipping, drying, roasting2O3/TiO2Presoma；The MnO under electrostatic attraction force effect4 ‑Ion selectivity is adsorbed on Rh2O3Rh Mn/TiO are made after drying and roasting for grain surface2Catalyst.Catalyst of the present invention increases the interfacial contact of Rh and Mn, significantly improves the utilization rate of Rh under the premise of influencing smaller to carrier surface.When Rh load capacity is identical, Rh Mn/TiO of the present invention2Catalyst has the selectivity of higher CO conversion ratios and C2 oxygenatedchemicals.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of catalyst for synthesis gas C2 oxygenatedchemicals
And preparation method thereof.
Background technology
Since oil shock of 1973 crisis, each industrial country of the world is all in the resource for seeking other alternative oil, naturally
Gas then becomes first choice.The comprehensive utilization of natural gas mainly converts methane to synthesis gas, and realizes synthesis on this basis
The industrialization of ammonia, synthetic oil, synthesizing methanol.And it synthesizes C2 oxygenatedchemicals and remains in pilot scale level.How high activity is developed
Catalyst with selectivity is that the emphasis of synthesis gas C2 oxygenatedchemicals is also difficult point.There is Rh moderate carbon monoxide to dissociate
Ability be inserted into ability, especially add transition elements Mn as auxiliary agent after, the interaction between Rh-MnO can be improved it is oxygen-containing in
Between product stability, in synthesis gas C2 oxygenatedchemicals have it is higher activity with selectivity.But Rh prices are high
Expensive, higher load capacity can increase the cost in practical application.Therefore, enhance the interaction between Rh and MnO, improve the original of Rh
Sub- utilization rate is to reduce an effective way of catalyst cost.
The rhodium base catalyst for being presently used for synthesis gas C2 oxygenatedchemicals mostly uses active component and auxiliary agent co-impregnation
It is prepared by method.A kind of method by synthesis of gas produced low-carbon oxygenatedchemicals that Chinese patent CN102294260A is announced uses
MCM-48 is carrier, and radium chloride, manganese nitrate, ferric nitrate, lithium nitrate wiring solution-forming are carried out incipient impregnation, are after drying and roasting
It can.Use mesopore silicon oxide for carrier in Chinese patent CN101992099A, equally by radium chloride, manganese nitrate, ferric nitrate, nitric acid
Lithium wiring solution-forming carries out incipient impregnation.Prepare that catalyst is easily operated using co-impregnation, but be difficult to avoid that there are some
Disadvantage：Rh crystal grain is uniformly dispersed in carrier surface with MnO crystal grain, and interfacial contact between the two is limited.It is not in contact with MnO
Activity and the selectivity of Rh be far from the height of the interfaces Rh-MnO, this reduces the utilization rate of Rh atoms to a certain extent；
Then carrier surface can be caused to be covered by excessive MnO to increase the interfacial contact area of Rh-MnO by further increasing the load capacity of Mn
Lid reduces catalyst activity.Therefore, the preparation condition of catalyst how is controlled, reduces the influence to carrier itself as possible, into one
The utilization rate of Rh atoms can be improved in the interfacial contact of step enhancing Rh and MnO, becomes the activity and selectivity for improving catalyst.
Invention content
The present invention is limited using the interfacial contact of Rh-MnO in the catalyst of co-impregnation preparation for the prior art, and Rh is former
The low problem of sub- utilization rate provides a kind of Rh-Mn/TiO prepared using Electrostatic Absorption method2Catalyst, and using co-impregnation
Catalyst prepared by method is compared, Rh-Mn/TiO of the present invention2Catalyst is identical with higher CO turns in Rh load capacity
The selectivity of rate and C2 oxygenatedchemicals.
The purpose of the present invention is achieved through the following technical solutions：
A kind of catalyst for synthesis gas C2 oxygenatedchemicals, including carrier, active component and auxiliary agent；The load
Body is nano-TiO2, the active component is Rh, and the auxiliary agent is Mn；The load capacity of Rh is 0.05-5%, the load of Mn
Amount is 0.5-10%.
Preferably, the load capacity of Rh is 0.5-3% in the catalyst, and the load capacity of Mn is 0.5-5%.
It is further preferred that the load capacity of Rh is 1-2% in the catalyst, the load capacity of Mn is 1-2.5%.
The nano-TiO2Average grain diameter be 20-50nm.
It is of the present invention to be used for synthesis gas C2 oxygenatedchemicals catalyst, it is made from following preparation method：It will
Nano-TiO2It is uniformly mixed with rhodium chloride solution, Rh is made in sonicated, dry successively, roasting2O3/TiO2Predecessor；It will
Rh2O3/TiO2Predecessor is placed in the permanganate solution of strong acid acidification, and shaking table concussion, filtering, dry, roasting are prepared
Rh-Mn/TiO2Catalyst.
It is a further object to provide the preparation sides for synthesis gas C2 oxygenatedchemicals catalyst
Method includes the following steps：
Step (1) prepares Rh2O3/TiO2Predecessor：By nano-TiO2It is uniformly mixed with rhodium chloride solution, successively through ultrasound
Rh is made in processing, dry, roasting2O3/TiO2Predecessor；
Step (2), Electrostatic Absorption method prepare catalyst：By Rh2O3/TiO2Predecessor is placed in the permanganate of strong acid acidification
In solution, Rh-Mn/TiO is prepared in shaking table concussion, filtering, dry, roasting2Catalyst.
In step (1), the rhodium chloride solution is with one kind in deionized water, methanol, ethyl alcohol, normal propyl alcohol, n-butanol
Or it a variety of is formulated for solvent.
The temperature of the supersound process is room temperature, power 50-600W, time 20-100min.
The drying condition is to be dried in vacuo 0.5-12h at 80-120 DEG C.
The roasting condition is to roast 2-6h at 300-500 DEG C.
In step (2), the pH of the permanganate solution of the acidification is 1.5-6.0.
The permanganate is one or more in potassium permanganate, high manganese lithium, sodium permanganate, ammonium permanganate.
The strong acid is one or more in sulfuric acid, hydrochloric acid, nitric acid；Preferably in the concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid
It is one or more.
The concussion frequency of the shaking table is 50-300rpm, and temperature is 20-80 DEG C, time 0.5-3h.The drying
Condition is to be dried in vacuo 0.5-12h at 80-120 DEG C.The roasting condition is to roast 2-6h at 350-500 DEG C.
The actual negative carrying capacity of Rh and Mn uses inductive coupling plasma emission spectrograph (ICP- in catalyst of the present invention
OES it) measures.
It is a further object to provide the method that the catalyst is used for synthesis gas C2 oxygenatedchemicals, packets
It includes：Synthesis gas is passed through into the reactor equipped with catalyst of the present invention, the air speed 8000-15000h of synthesis gas-1, H in synthesis gas2With
The molar ratio of CO is 1-5:1, C2 oxygenatedchemicals is obtained by the reaction at 200-400 DEG C of temperature, pressure 1-5MPa.
Preferably, the air speed of the synthesis gas is 12000h-1。
Preferably, H in synthesis gas2Molar ratio with CO is 2:1.
Preferably, reaction temperature is 320 DEG C, pressure 5.0MPa.
The pre-treatment of catalyst of the present invention：Catalyst tablet forming is crushed, is sized to 20-40 mesh, loaded on reaction
Pipe constant temperature zone；It is passed through hydrogen and carries out reduction treatment, reducing condition is：350 DEG C of temperature, hydrogen gas space velocity 1000h-1, recovery time 3h,
Pressure 0.3MPa.
The C2 oxygenatedchemicals is at least one of acetaldehyde, ethyl alcohol, acetic acid.
Beneficial effects of the present invention：
The present invention prepares catalyst using Electrostatic Absorption method, and the pH value for adjusting permanganate solution is 1.5-6.0, is located at and carries
Body TiO2Point of zero electric charge (TiO2Point of zero electric charge be 3.7 or so) near value, while passing through adjustment effect time, electrostatic attraction
MnO under force effect4 -Ion selectivity is adsorbed on Rh2O3Grain surface, to obtain efficiently urging for Rh-MnO strong interactions
Agent.Compared with traditional co-impregnation, the present invention increases Rh and Mn species under the premise of influencing smaller to carrier surface
Interfacial contact greatly improves the utilization rate of noble metal Rh.When Rh load capacity is identical, prepared by Electrostatic Absorption method of the present invention
Rh-Mn/TiO2Catalyst has the selectivity of higher CO conversion ratios and C2 oxygenatedchemicals.
Synthesis gas C2 oxygenatedchemicals is used for using catalyst of the present invention, the conversion ratio of CO is generated in 10-22%
The C2 oxygen-containing mixtures that acetaldehyde, ethyl alcohol, acetic acid form in product account for 47-72%, and methanol accounts for 0.6-1.3%, and other is hydro carbons.
Description of the drawings
Fig. 1 is that Electrostatic Absorption method prepares catalyst schematic diagram.
Specific implementation mode
Technical scheme of the present invention is specifically described with reference to embodiment.
Embodiment 1
0.1279g radium chlorides are dissolved in 5mL deionized waters by step (1), and it is 20-50nm's to take 5.0g average grain diameters
Titanium dioxide is placed in rhodium chloride solution, room temperature ultrasound 50min, ultrasonic power 100W；It is dried in vacuo 2h at 80 DEG C, 300 DEG C
Lower roasting 5h, obtains Rh2O3/TiO2Predecessor.
1.5g ammonium permanganates are dissolved in 500mL deionized waters by step (2), and it is 4.5 to be used in combination concentrated hydrochloric acid to adjust pH value of solution；
By 2.0g Rh2O3/TiO2Predecessor is placed in the ammonium permanganate solution after concentrated hydrochloric acid acidification, and shaking table shakes 0.5h, shake at 20 DEG C
It is 200rpm to swing frequency；Mixture filters, and is dried in vacuo 0.5h at 100 DEG C, 3h is roasted at 350 DEG C.It is negative that Rh is measured through ICP-OES
Carrying capacity is that 1.0% (Rh atoms account for TiO2Mass percent, similarly hereinafter), Mn load capacity is that 0.5% (Mn atoms account for TiO2Quality
Percentage, similarly hereinafter), it is denoted as 1.0Rh-0.5Mn/TiO2。
Embodiment 2
0.1917g radium chlorides are dissolved in 2.0g methanol by step (1), and it is the nanometer of 20-50nm to take 5.0g average grain diameters
Titanium dioxide is placed in rhodium chloride solution, room temperature ultrasound 80min, ultrasonic power 200W；It is dried in vacuo 3h at 100 DEG C, 350 DEG C
Lower roasting 6h, obtains Rh2O3/TiO2Predecessor.
2.0g high manganese lithiums are dissolved in 500mL deionized waters by step (2), and it is 3.1 to be used in combination the concentrated sulfuric acid to adjust pH value of solution；
By 2.5g Rh2O3/TiO2Predecessor is placed in the high manganese lithium solution after concentrated sulfuric acid acidification, and shaking table shakes 0.5h, shake at 40 DEG C
It is 250rpm to swing frequency；Mixture filters, and is dried in vacuo 10h at 110 DEG C, 5h is roasted at 430 DEG C.It is negative that Rh is measured through ICP-OES
Carrying capacity is that 1.5%, Mn load capacity is 1.0%, is denoted as 1.5Rh-1.0Mn/TiO2。
Embodiment 3
0.0640g radium chlorides are dissolved in 3.0g normal propyl alcohols by step (1), and it is the two of 20-50nm to take 5.0g average grain diameters
Titanium oxide is placed in rhodium chloride solution, room temperature ultrasound 90min, ultrasonic power 100W；2h is dried in vacuo at 120 DEG C, at 350 DEG C
3h is roasted, Rh is obtained2O3/TiO2Predecessor.
2.2g high manganese lithiums are dissolved in 500mL deionized waters by step (2), and it is 1.5 to be used in combination concentrated hydrochloric acid to adjust pH value of solution；
By 2.5g Rh2O3/TiO2Predecessor is placed in the high manganese lithium solution of concentrated hydrochloric acid acidification, and shaking table shakes 2.0h, concussion at 70 DEG C
Frequency is 150rpm；Mixture filters, and is dried in vacuo 1h at 90 DEG C, 3h is roasted at 380 DEG C.Rh load capacity is measured through ICP-OES
It is 1.5% for 0.5%, Mn load capacity, is denoted as 0.5Rh-1.5Mn/TiO2。
Embodiment 4
0.1267g radium chlorides are dissolved in 2.0g ethyl alcohol by step (1), and it is the dioxy of 20-50nm to take 5.0g average grain diameters
Change titanium to be placed in rhodium chloride solution, room temperature ultrasound 60min, ultrasonic power 200W；It is dried in vacuo 8h at 110 DEG C, is roasted at 400 DEG C
5h is burnt, Rh is obtained2O3/TiO2Predecessor.
1.0g potassium permanganate is dissolved in 500mL deionized waters by step (2), and it is 5.6 to be used in combination concentrated hydrochloric acid to adjust pH value of solution；
By 2.5g Rh2O3/TiO2Predecessor is placed in the liquor potassic permanganate after concentrated hydrochloric acid acidification, and shaking table shakes 2.5h, shake at 30 DEG C
It is 200rpm to swing frequency；Mixture filters, and is dried in vacuo 4h at 100 DEG C, 4h is roasted at 500 DEG C.Rh loads are measured through ICP-OES
It is 0.5% that amount, which is 1.0%, Mn load capacity, is denoted as 1.0Rh-0.5Mn/TiO2。
Embodiment 5
0.2554g radium chlorides are dissolved in 4.0g n-butanols by step (1), and it is the two of 20-50nm to take 5.0g average grain diameters
Titanium oxide is placed in rhodium chloride solution, room temperature ultrasound 80min, ultrasonic power 500W；6h is dried in vacuo at 110 DEG C, at 450 DEG C
3h is roasted, Rh is obtained2O3/TiO2Predecessor.
1.3g sodium permanganates are dissolved in 500mL deionized waters by step (2), and it is 5.9 to be used in combination concentrated nitric acid to adjust pH value of solution；
By 3.0gRh2O3/TiO2Predecessor is placed in the sodium permanganate solution of concentrated nitric acid acidification, and shaking table shakes 1.0h, concussion frequency at 50 DEG C
Rate is 300rpm；Mixture filters, and is dried in vacuo 2h at 120 DEG C, 6h is roasted at 410 DEG C.Measuring Rh load capacity through ICP-OES is
2.0%, Mn load capacity are 1.0%, are denoted as 2.0Rh-1.0Mn/TiO2。
Embodiment 6
0.1915g radium chlorides are dissolved in 3.0g ethyl alcohol by step (1), and it is the dioxy of 20-50nm to take 5.0g average grain diameters
Change titanium to be placed in rhodium chloride solution, room temperature ultrasound 100min, ultrasonic power 300W；3h is dried in vacuo at 100 DEG C, at 500 DEG C
2h is roasted, Rh is obtained2O3/TiO2Predecessor.
3.0g sodium permanganates are dissolved in 500mL deionized waters by step (2), and it is 4.0 to be used in combination the concentrated sulfuric acid to adjust pH value of solution；
By 2.0g Rh2O3/TiO2Predecessor is placed in the sodium permanganate solution of concentrated sulfuric acid acidification, and shaking table shakes 2.0h, concussion at 60 DEG C
Frequency is 200rpm；Mixture filters, and is dried in vacuo 10h at 120 DEG C, 6h is roasted at 350 DEG C.Rh loads are measured through ICP-OES
It is 2.5% that amount, which is 1.5%, Mn load capacity, is denoted as 1.5Rh-2.5Mn/TiO2。
Embodiment 7
0.1277g radium chlorides are dissolved in 5.0g methanol by step (1), and it is the dioxy of 20-50nm to take 5.0g average grain diameters
Change titanium to be placed in rhodium chloride solution, room temperature ultrasound 50min, ultrasonic power 500W；It is dried in vacuo 8h at 120 DEG C, is roasted at 350 DEG C
6h is burnt, Rh is obtained2O3/TiO2Preceding object.
3.0g ammonium permanganates are dissolved in 500mL deionized waters by step (2), and it is 2.7 to be used in combination concentrated hydrochloric acid to adjust pH value of solution；
By 2.0g Rh2O3/TiO2Predecessor is placed in the ammonium permanganate solution of concentrated hydrochloric acid acidification, and shaking table shakes 1.2h, concussion at 20 DEG C
Frequency is 200rpm；Mixture filters, and is dried in vacuo 3h at 90 DEG C, 4h is roasted at 420 DEG C.Rh load capacity is measured through ICP-OES
It is 2.0% for 1.0%, Mn load capacity, is denoted as 1.0Rh-2.0Mn/TiO2。
Embodiment 8
0.1281g radium chlorides are dissolved in 4.0mL deionized waters by step (1), and it is 20-50nm to take 5.0g average grain diameters
Titanium dioxide be placed in rhodium chloride solution, room temperature ultrasound 100min, ultrasonic power 200W；It is dried in vacuo 2h at 80 DEG C, 400
5h is roasted at DEG C, obtains Rh2O3/TiO2Predecessor.
1.4g ammonium permanganates are dissolved in 500mL deionized waters by step (2), and it is 3.8 to be used in combination the concentrated sulfuric acid to adjust pH value of solution；
By 5.0g Rh2O3/TiO2Predecessor is placed in the ammonium permanganate solution of concentrated sulfuric acid acidification, and shaking table shakes 3.0h, concussion at 50 DEG C
Frequency is 250rpm；Mixture filters, and is dried in vacuo 5h at 100 DEG C, 3h is roasted at 460 DEG C.Rh load capacity is measured through ICP-OES
It is 0.5% for 1.0%, Mn load capacity, is denoted as 1.0Rh-0.5Mn/TiO2。
Comparative example 1
0.1409g radium chlorides and 0.2510g ammonium permanganates are dissolved in 5.0g methanol, it is 20- to take 5.0g average grain diameters
The titanium dioxide of 50nm is placed in mixed solution, room temperature ultrasound 50min, ultrasonic power 500W；It is dried in vacuo 3h at 90 DEG C,
4h is roasted at 420 DEG C.It is 1.0%, Mn load capacity is 2.0% to measure Rh load capacity through ICP-OES, is denoted as 1.0Rh-2.0Mn/
TiO2。
Comparative example 2
0.2550g radium chlorides and 0.1039g ammonium permanganates are dissolved in 4.0g n-butanols, take the 5.0g average grain diameters to be
The titanium dioxide of 20-50nm is placed in mixed solution, room temperature ultrasound 80min, ultrasonic power 500W；It is dried in vacuo at 120 DEG C
4h roasts 6h at 410 DEG C.It is 2.0%, Mn load capacity is 1.0% to measure Rh load capacity through ICP-OES, is denoted as 2.0Rh-
1.0Mn/TiO2。
Comparative example 3
0.1931g radium chlorides and 0.3115g ammonium permanganates are dissolved in 3.0g ethyl alcohol, it is 20- to take 5.0g average grain diameters
The titanium dioxide of 50nm is placed in mixed solution, room temperature ultrasound 100min, ultrasonic power 300W；It is dried in vacuo at 120 DEG C
10h roasts 6h at 350 DEG C.It is 1.5%, Mn load capacity is 2.5% to measure Rh load capacity through ICP-OES, is denoted as 1.5Rh-
2.5Mn/TiO2。
Synthesis gas C2 oxygenatedchemicals is used for using the catalyst that embodiment and comparative example is prepared, specially：It takes
2g catalyst tablet formings are crushed, are sized to 20-40 mesh；It is 19mm to take internal diameter, and the reaction tube of pipe range 700mm fills catalyst
In reaction tube constant temperature zone.Catalyst reduction condition is：350 DEG C of temperature, hydrogen gas space velocity 1000h-1, recovery time 3h, pressure
0.3MPa；Reaction condition is：320 DEG C, pressure 5.0MPa of temperature, synthesis gas air speed 12000h-1, H2/ CO=2.
1 catalyst performance of table is investigated
The MnO under electrostatic attraction force effect4 -Ion selectivity is adsorbed on Rh2O3Rh- is made after drying and roasting for grain surface
Mn/TiO2Catalyst.As shown in Table 1, compared with traditional co-impregnation, this method is influencing carrier surface smaller premise
Under, the interfacial contact of Rh and Mn are increased, the utilization rate of metal Rh is greatly improved, when Rh load capacity is identical, electrostatic is inhaled
Rh-Mn/TiO prepared by attached method2Catalyst is remarkably improved the selectivity of CO conversion ratios and C2 oxygenatedchemicals.
Claims (10)
1. a kind of catalyst for synthesis gas C2 oxygenatedchemicals, it is characterised in that the catalyst is Rh-Mn/TiO2
Catalyst, with nano-TiO2For carrier, using Rh as active component, using Mn as auxiliary agent；The load capacity of Rh is 0.05-5%, and Mn's is negative
Carrying capacity is 0.5-10%.
2. catalyst according to claim 1, it is characterised in that the load capacity of Rh is 0.5-3% in the catalyst,
The load capacity of Mn is 0.5-5%；Preferably, the load capacity of Rh is 1-2% in the catalyst, and the load capacity of Mn is 1-
2.5%.
3. catalyst according to claim 1, it is characterised in that the nano-TiO2Average grain diameter be 20-50nm.
4. a kind of preparation method of the catalyst described in claim 1 for synthesis gas C2 oxygenatedchemicals, feature exist
In including the following steps：
Step (1) prepares Rh2O3/TiO2Predecessor：By nano-TiO2It is uniformly mixed with rhodium chloride solution, sonicated successively,
Rh is made in dry, roasting2O3/TiO2Predecessor；
Step (2), Electrostatic Absorption method prepare catalyst：By Rh2O3/TiO2Predecessor is placed in the permanganate solution of strong acid acidification
In, shaking table concussion, filtering, dry, roasting obtain Rh-Mn/TiO2Catalyst.
5. preparation method according to claim 4, it is characterised in that the rhodium chloride solution with deionized water, methanol,
One or more in ethyl alcohol, normal propyl alcohol, n-butanol are formulated for solvent.
6. preparation method according to claim 4, it is characterised in that in step (1), the power of supersound process is 50-
600W, time 20-100min；Drying condition is to be dried in vacuo 0.5-12h at 80-120 DEG C；Roasting condition is 300-500 DEG C
Lower roasting 2-6h.
7. preparation method according to claim 4, it is characterised in that in step (2), the permanganate of the acidification is molten
The pH of liquid is 1.5-6.0.
8. preparation method according to claim 4, it is characterised in that in step (2), the permanganate is permanganic acid
It is one or more in potassium, high manganese lithium, sodium permanganate, ammonium permanganate；The strong acid is sulfuric acid, hydrochloric acid, one in nitric acid
Kind is a variety of.
9. preparation method according to claim 4, it is characterised in that in step (2), the concussion frequency of shaking table is 50-
300rpm, temperature are 10-80 DEG C, time 0.5-3h；Drying condition is to be dried in vacuo 0.5-12h at 80-120 DEG C；Roast item
Part is to roast 2-6h at 350-500 DEG C.
10. the method that catalyst described in claim 1 is used for synthesis gas C2 oxygenatedchemicals, it is characterised in that including：It will
Synthesis gas is by being filled with the reactor of catalyst described in claim 1, the air speed 8000-15000h of synthesis gas-1, synthesis gas
Middle H2Molar ratio with CO is 1-5:1, C2 oxygenatedchemicals is obtained by the reaction at 200-400 DEG C of temperature, pressure 1-5MPa.
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| CN111375445A (en) * | 2018-12-29 | 2020-07-07 | 中化近代环保化工(西安)有限公司 | Preparation method and application of molecular sieve-loaded manganese-based denitration catalyst |
| CN111659395A (en) * | 2020-05-26 | 2020-09-15 | 北京化工大学 | Preparation method and application of foamed iron-based catalyst with high all-olefin selectivity |
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