CN110354852A - A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound - Google Patents
A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound Download PDFInfo
- Publication number
- CN110354852A CN110354852A CN201810255401.XA CN201810255401A CN110354852A CN 110354852 A CN110354852 A CN 110354852A CN 201810255401 A CN201810255401 A CN 201810255401A CN 110354852 A CN110354852 A CN 110354852A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- support type
- base catalyst
- active component
- synthesis gas
- 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.)
- Granted
Links
- 239000010948 rhodium Substances 0.000 title claims abstract description 151
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 115
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 235000019441 ethanol Nutrition 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 88
- 239000002105 nanoparticle Substances 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 19
- 229910000085 borane Inorganic materials 0.000 claims description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 14
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 8
- 229960004756 ethanol Drugs 0.000 description 35
- 239000007789 gas Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 28
- 238000001035 drying Methods 0.000 description 20
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 19
- 239000012752 auxiliary agent Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 239000011565 manganese chloride Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 9
- GKFJEDWZQZKYHV-UHFFFAOYSA-N borane;2-methylpropan-2-amine Chemical compound B.CC(C)(C)N GKFJEDWZQZKYHV-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 tert-butylamine boron Alkane Chemical class 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZTVIKZXZYLEVOL-DGKWVBSXSA-N 2-hydroxy-2-phenylacetic acid [(1R,5S)-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] ester Chemical group C([C@H]1CC[C@@H](C2)N1C)C2OC(=O)C(O)C1=CC=CC=C1 ZTVIKZXZYLEVOL-DGKWVBSXSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 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
-
- B01J35/393—
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
-
- 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
Abstract
The present invention provides a kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound.The support type rhodium base catalyst includes main active component and carrier；Wherein, the main active component contains rhodium element and manganese element, and the weight percentage of rhodium element and manganese element in support type rhodium base catalyst is 0.01~20.0wt%；The carrier is selected from least one of silica, aluminium oxide, titanium oxide.By the support type rhodium base catalyst of particle uniform, controllable provided by the invention, in fixed bed reactors, under certain temperature and pressure and this catalyst action, H2/ CO can high activity, be converted into ethyl alcohol, acetaldehyde and acetic acid with high selectivity.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to one kind is used for synthesis gas C2Oxidiferous particle
The support type rhodium base catalyst of uniform, controllable relates more specifically to one kind by raw material of synthesis gas and is converted into ethyl alcohol, acetaldehyde and second
The support type rhodium base catalyst and preparation method thereof of acid.
Background technique
Ethyl alcohol is not only important solvent and industrial chemicals, or the ideal free of contamination vehicle fuel of high-octane rating and its
Additive.China's ethyl alcohol annual capacity is about 15,000,000 tons or so, and yield is 10,000,000 tons.Currently, production ethyl alcohol technology path is
Starchy material (such as corn) or saccharine material (such as sugarcane) fermentation method.The alcohol fuel gasoline (E10) of addition 10%, can subtract
The 30% of few vehicle exhaust CO discharge amount, the 40% of hydro carbons discharge amount, while reducing CO2With the discharge of oxynitrides.At present
For the industrial process of ethyl alcohol based on grain fermentation method, grain fermentation method one ton of ethyl alcohol of every production need to consume 3.3 tons of corns.I
State is populous, and cultivated area is insufficient, and the grain demand of China still has 0.25~0.35 hundred million tons of notch.With
Domestic Automotive Industry flourishes and its atmosphere pollution that is on the rise, it is contemplated that the dehydrated alcohol of E10 gasoline consumption is up to
1000~15,000,000 tons/year, and produce so a large amount of grain fermenting alcohol and need a large amount of cultivated area.Alcohol industry is for I
State's environmental emission organic pollutant highest, the pollution serious industry of environment, the pollution of alcohol waste water are food and fermentation work
One of the pollution sources of industry most serious.1 ton of alcohol of every production generates 12~15 tons of alcohol mg/L waste water, and wherein COD is up to 4 × 104mg/
L~7 × 104Mg/L, BOD are up to 3 × 104Mg/L~5 × 104mg/L。
China's oil scarcity of resources, and coal and gas reserves relative abundance.From the angle of the utilization of resources and environmental protection
Degree sees that the coal and proper utilization of natural gas of active development high effect cleaning are with important strategic importance and before being widely applied
Scape.With synthesis gas (H2/ CO) conversion based on C-1 chemistry chemical industry be more practicable substitution petroleum obtain oil plant and
The approach of chemicals.Synthesis gas ethyl alcohol and other advanced oxycompounds are always an important subject of C-1 chemistry.
For the oxycompound of synthesis gas ethyl alcohol directly processed because its route is short, equipment investment is low, is constantly subjected to pay close attention to.Its bottleneck is to urge at present
The cost and efficiency of agent.Synthesis gas ethyl alcohol directly processed refers to synthesis with C such as ethyl alcohol2+OH be principal product low carbon mixed alcohol or
Oxycompound is mixed, hydrogen is then further added or is isolated and purified.
According to C2The CO of oxycompound production is inserted into mechanism, for synthesis gas C2Oxycompound catalyst must have with
Lower property: it can adsorb and dissociate CO；The ability for dissociating CO cannot be too strong, to guarantee the progress of CO insertion；Moderate plus hydrogen
Performance is conducive to by force very much the generation of methane and methanol, too weak to cause catalyst activity too low.In numerous metals, CO is dissociated
Moderate Rh also shows moderate alkylation activity.Due to these characteristics of metal Rh, have both as synthesis gas Gao Xuan
Selecting property synthesizes C2The necessary condition of oxycompound catalyst is the C such as synthesis gas ethyl alcohol directly processed2Oxycompound desired activities component.
Absorption and priming reaction mechanism of the CO on Rh base catalyst can summarize following steps: (1) CO is in Rh0Absorption
And it dissociates and is hydrogenated to CH3/CH2Species will form a kind of CO of tilting absorption if there is oxytropism oxides additive exists
Species, CO carbon teminal is adsorbed on Rh, and oxygen end is adsorbed on auxiliary agent, to weaken C=O key, promotes CO dissociation.(2)Rh+
The CO of non-adsorbed dissociation in active sites is shifted and insertion surface alkyl chain, forms Surface acyl species, is then hydrogenated to C2Contain
Oxide.(3) in Rh0On be hydrogenated to Main By product methane.CO is hydrogenated to C2Oxycompound is that a structure sensitive is anti-
It answers, Rh dispersion degree influences catalyst activity very big.
The method for adjusting Rh partial size generally have control Rh load capacity, adjust impregnated granules granularity, micro emulsion method prepare catalyst,
The surface-hydrophobicized processing of carrier.Alcohols can lead to Silica Surface by being dehydrated to form alkoxylation species with Silica Surface Si-OH
Hydrophobicity enhancing.Metal in dry or roasting process can be prevented by space segmentation effect by being grafted onto the alkoxy on Silica Surface
The sintering of particle.Reagent alkyl chain used in silicic acid anhydride is longer, and metallic particles is smaller.Although above-mentioned Rh size controlling can
To synthesize the catalyst of certain particle size range, but Rh particle diameter distribution is wider, for uniform the being precisely controlled property of particle size
It is poor.For Rh efficiency and C2Oxycompound, which selectively improves, certain restriction effect.
Summary of the invention
The purpose of the present invention is to provide one kind to be used for synthesis gas C2The support type of oxidiferous particle uniform, controllable
Rhodium base catalyst.Rhodium nanoparticle in the catalyst containing uniform particle sizes, the catalyst are used for synthesis gas C2Oxycompound
Reaction, can high activity, be converted into ethyl alcohol C with high selectivity2Oxycompound, CO Hydrogenation are significantly stronger than traditional catalyst.
The support type rhodium base catalyst, which is characterized in that the support type rhodium base catalyst include main active component and
Carrier；Wherein, the main active component contains rhodium element and manganese element, and rhodium element and manganese element are in support type rhodium base catalyst
Weight percentage be 0.01~20.0wt%；The carrier is selected from least one of silica, aluminium oxide, titanium oxide.
Optionally, the specific surface area of the silica is 5~400m2/ g, average pore size are 1~200nm.
Optionally, the specific surface area of the silica is 10~350m2/ g, average pore size are 5~150nm.
Preferably, the specific surface area of the silica is 5~300m2/ g, average pore size are 10~80nm.
Optionally, the specific surface area of the aluminium oxide is 20~300m2/ g, average pore size are 5~100nm.
Optionally, the specific surface area of the aluminium oxide is 30~250m2/ g, average pore size are 10~100nm
Preferably, the specific surface area of the aluminium oxide is 50~200m2/ g, average pore size are 10~80nm.
Optionally, the specific surface area of the titanium oxide is 20~100m2/ g, average pore size are 10~100nm.
Optionally, the specific surface area of the titanium oxide is 30~90m2/ g, average pore size are 20~100nm
Preferably, the specific surface area of the titanium oxide is 50~90m2/ g, average pore size are 20~80nm.
Preferably, weight percentage of the rhodium element in support type rhodium base catalyst is 0.1 in the main active component
~10.0wt%.It is further preferred that weight percent of the rhodium element in support type rhodium base catalyst in the main active component
Content is 0.5~5.0wt%.
Preferably, weight percentage of the manganese element in support type rhodium base catalyst is 0.1 in the main active component
~10.0wt%.It is further preferred that weight percent of the manganese element in support type rhodium base catalyst in the main active component
Content is 0.5~5.0wt%.
Preferably, rhodium element exists in the form of rhodium nanoparticle in the main active component；The rhodium nanoparticle
Average grain diameter D50A certain value between 1~20nm, (D90-D10)/D50≤1.0.It is further preferred that the rhodium nanoparticle
Average grain diameter D50A certain value between 1~10nm, (D90-D10)/D50≤0.7.It is further preferred that the rhodium nanometer
The average grain diameter D of particle50A certain value between 1~10nm, (D90-D10)/D50≤0.5.It is again it is further preferred that described
The average grain diameter D of rhodium nanoparticle50A certain value between 1~7.5nm, (D90-D10)/D50≤0.5.Again still more preferably
Ground, the average grain diameter D of the rhodium nanoparticle50A certain value between 1~7.5nm, (D90-D10)/D50≤0.3.As one kind
Embodiment, the average grain diameter D of the rhodium nanoparticle50A certain value between 1~7.5nm, 0.5≤(D90-D10)/D50≤
1.0。
As a kind of specific embodiment, the support type rhodium base catalyst is by main active component and carrier two parts group
At main active component is rhodium and transition metal promoter Mn, and weight is the 0.01~20.0% of catalyst weight；Carrier is oxidation
Silicon, aluminium oxide, titanium oxide, the specific surface area of silica is 5~400m in carrier2/ g, average pore size is 1~200nm, in carrier
The specific surface area of aluminium oxide is 20~300m2/ g, average pore size are 5~100nm, in carrier the specific surface area of titanium oxide be 20~
100m2/ g, average pore size are 10~100nm.Preferably, main active component rhodium weight is to urge in the support type rhodium base catalyst
The 0.1~10.0% of agent weight.Preferably, transition metal promoter is in main active component in the support type rhodium base catalyst
Mn, weight are the 0.1~10.0% of catalyst weight.
Preferably, carrier is silica, aluminium oxide, titanium oxide in the support type rhodium base catalyst；Silica in carrier
Specific surface area be 10~350m2/ g, average pore size are 5~150nm；The specific surface area of aluminium oxide is 30~250m in carrier2/
G, average pore size are 10~100nm；The specific surface area of titanium oxide is 30~90m in carrier2/ g, average pore size are 20~100nm.
According to the another aspect of the application, provide the preparation method of the support type rhodium base catalyst, can particle it is uniform
Controllable prepares the support type rhodium base catalyst.This method utilizes the protective effect of surfactant in liquid phase reactor and goes back
The reduction of former agent, the uniform adjustable nanometer rhodium particle of synthesis particle, the nano particle being then dissolved in organic solvent
It is supported on carrier, a small amount of protective agent is removed by reduction and obtains evengranular nanometer Rh catalyst, CO Hydrogenation is bright
It is aobvious to be better than preparation catalyst.
The method for preparing the support type rhodium base catalyst, which is characterized in that at least include the following steps:
A) Mn is carried on carrier using infusion process, obtains the carrier of load Mn；
B) rhodium nanoparticle is obtained；
C) using infusion process by rhodium nanometer particle load on the carrier of load Mn, obtaining support type rhodium base catalysis
Agent.
As an implementation, in step b) rhodium nanoparticles preparation method the following steps are included:
Solution I containing organic rhodium complex is mixed with the solution II for closing borine containing organic amine, in 190~240 DEG C
Reaction is no less than 2 hours to get the rhodium nanoparticles are arrived.
As an implementation, in step b) rhodium nanoparticles preparation method the following steps are included:
Acetylacetone,2,4-pentanedione rhodium is dissolved in oleyl amine and obtains solution I；
Tert-butylamine borine is dissolved in oleyl amine and obtains solution II；
Solution I is heated to 190~240 DEG C and solution I is added in solution II, after reacting 2~6h, is cooled to 40~80
DEG C, the rhodium nanoparticle is arrived after washed, separation.
As a kind of specific embodiment, the method for preparing the support type rhodium base catalyst includes at least following step
Rapid: a certain amount of acetylacetone,2,4-pentanedione rhodium is dissolved in oleyl amine, is heated to 190~240 DEG C, is completely dissolved；A certain amount of tert-butylamine boron
Alkane is dissolved in oleyl amine, ultrasonic dissolution.It will be molten dissolved with the oleyl amine of acetylacetone,2,4-pentanedione rhodium dissolved with the addition of the oleyl amine solution of tert-butylamine borine
Liquid is kept for 190~240 DEG C, persistently stirs 2~6h, is cooled to 40~80 DEG C, and ethyl alcohol, centrifugation is added, and product is dissolved with hexamethylene
Ethyl alcohol is added again afterwards, is centrifuged again, obtains Rh nano particle and is dissolved with hexamethylene, dipping has loaded the carrier of Mn, and solvent steams
After hair, 120 DEG C of drying.
According to the another aspect of the application, a kind of synthesis gas C is provided2Oxidiferous method, i.e., the described support type rhodium
Base catalyst and/or the support type rhodium base catalyst being prepared according to the method are in synthesis gas C2Answering in oxycompound
With.
The synthesis gas C2Oxidiferous method, which is characterized in that state the support type rhodium base catalyst, basis
At least one of support type rhodium base catalyst that method is prepared is after reduction pretreatment, and synthesis gas haptoreaction,
Prepare C2Oxycompound；
The C2Oxycompound is selected from least one of ethyl alcohol, acetaldehyde, acetic acid.
As an implementation, the condition of the reduction pretreatment are as follows: used at a temperature of 400~500 DEG C and contain H2
Gas to 2~6h of the support type rhodium base catalyst prereduction.
As an implementation, the described and catalytic condition of synthesis gas are as follows: reaction temperature is 280~350 DEG C, instead
Answering pressure is 3.0~5.0MPa, and the volume space velocity of synthesis gas is 1500~1000h-1。
As a kind of specific embodiment, the described and catalytic condition of synthesis gas are as follows: reaction temperature is 280 DEG C,
Reaction pressure is 5.0MPa, synthesis gas (H2/ CO=2) volume space velocity be 5000h-1。
Preferably, the synthesis gas C2Oxidiferous reaction carries out in fixed bed reactors.
As a kind of specific embodiment, the synthesis gas C2Oxidiferous method, which is characterized in that H2Through adjusting
It is entered after pressure valve and mass flowmenter in the fixed bed reactors equipped with pellet type catalyst of the invention, at 400~500 DEG C
2~6h of catalyst pre-reduction is down to 280~350 DEG C of reaction temperature, then switches to synthesis gas, carries out CO hydrogenation reaction, conversion
For ethyl alcohol, acetaldehyde and acetic acid, reaction pressure is 3.0~5.0MPa, and synthesis gas air speed is 1500~1000h-1。
In the application, D50Indicate: the cumulative particle sizes percentile of sample reaches partial size corresponding when 50%.D50?
It is meso-position radius or median particle diameter, also illustrates that the average particle size of powder.D10Indicate: the cumulative particle sizes percentile of sample reaches
Corresponding partial size when 10%.D90Indicate: the cumulative particle sizes percentile of sample reaches partial size corresponding when 90%.
Beneficial effects of the present invention include but is not limited to:
(1) support type rhodium base catalyst provided by the present invention, the rhodium nano particle diameter in main active component is uniform, collection
It is distributed in suitable C middlely2The particle size interval that oxycompound generates, significantly improves Rh efficiency and C2Oxycompound selectivity.
(2) preparation method of support type rhodium base catalyst provided by the present invention, the rhodium nanoparticle in main active component
Size tunable, and preparation method is simple, is suitble to large-scale production.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise specified, raw materials and reagents used herein are all from commercially available, unprocessed direct use, used
Instrument and equipment uses the scheme and parameter of manufacturer's recommended.
In embodiment, the average grain diameter and size distribution of sample use Malvern Zetasizer S90 type laser particle analyzer
Measurement.
In embodiment, the average pore size and specific surface area of carrier are using nitrogen physisorption in Kang Ta company
It is measured on QuadraSorb SI4 type adsorption instrument.
In embodiment, synthesis gas C2In oxidiferous reaction evaluating, H2It is entered after pressure regulator valve and mass flowmenter
Catalyst pre-reduction in fixed bed reactors equipped with catalyst of the present invention after being down to reaction temperature, then switches to conjunction
At gas, CO hydrogenation reaction is carried out, ethyl alcohol, acetaldehyde and acetic acid are converted into.
1 catalyst sample D1 of comparative example#Preparation
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 0.037 gram of RhCl3.xH2O
(Rh 37wt%), is dissolved in 10mL deionized water, impregnates the silica support of 10 grams of load Mn auxiliary agents, and 120 DEG C dry, this
For infusion process Rh/Mn-SiO2Catalyst is denoted as catalyst sample D1#。
Embodiment 1
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 1 gram of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；10 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 1nm Rh nanoparticles solution
((D90-D10)/D50=1.0).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
1.0nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 1#。
Embodiment 2
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 2 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；20 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 2nm Rh nanoparticles solution
((D90-D10)/D50=0.5).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
2nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 2#。
Embodiment 3
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 4 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；40 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 3.5nm Rh nanoparticles solution
((D90-D10)/D50=0.5).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
3.5nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 3#。
Embodiment 4
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 8 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；80 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 4.5nm Rh nanoparticles solution
((D90-D10)/D50=0.8).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
4.5nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 4#。
Embodiment 5
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 16 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；160 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 5.5nm Rh nanoparticles solution
((D90-D10)/D50=1.0).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
5.5nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 5#。
Embodiment 6
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 32 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；320 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 6.5nm Rh nanoparticles solution
((D90-D10)/D50=0.7).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
6.5nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 6#。
Embodiment 7
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of Powdered silica carrier (specific surfaces
Product is 300m2/ g, average pore size 40nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 32 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 1L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；320 grams
Tert-butylamine borine is dissolved in 0.5L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione is added in tert-butylamine Borane solution
Rhodium solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, product is centrifugated, with 500mL hexamethylene
After dissolution, 500mL ethyl alcohol is added again, is centrifuged again, product 20mL hexamethylene dissolves, and it is molten to obtain 7.5nm Rh nano particle
Liquid ((D90-D10)/D50=1.0).The silica support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
7.5nmRh/Mn-SiO2Catalyst is denoted as catalyst sample 7#。
Embodiment 8
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of powdered alumina carrier (specific surfaces
Product is 100m2/ g, average pore size 30nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 4 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；40 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and obtains 3.5nm Rh nanoparticles solution
((D90-D10)/D50=0.8).The alumina support of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings are obtained
3.5nmRh/Mn-Al2O3Catalyst is denoted as catalyst sample 8#。
Embodiment 9
Weigh 0.022 gram of MnCl2, it is dissolved in 10mL deionized water, impregnates 10 grams of powdered titanium dioxide carrier (specific surfaces
Product is 50m2/ g, average pore size 60nm), after drying, 500 DEG C of Muffle kiln roasting 6h.Weigh 4 grams of acetylacetone,2,4-pentanedione rhodium (Rh
(acac)3), it is dissolved in oleyl amine 2L, is heated with stirring to 190 DEG C, continue to stir 1h, guarantee Rh (acac)3It is completely dissolved；40 grams
Tert-butylamine borine is dissolved in 1L oleyl amine, and ultrasonic disperse makes it completely dissolved.Acetylacetone,2,4-pentanedione rhodium is added in tert-butylamine Borane solution
Solution is kept for 190 DEG C, is continued to stir 2h, is cooled to 70 DEG C, 3L ethyl alcohol is added, and product is centrifugated, molten with 500mL hexamethylene
500mL ethyl alcohol is added again, is centrifuged again by Xie Hou, and product 20mL hexamethylene dissolves, and it is molten to obtain 3.5nm Rh nano particle
Liquid.The titanium dioxide carrier of 10 grams of load Mn auxiliary agents is impregnated, after solvent dries in the shade, 120 DEG C of dryings obtain 3.5nmRh/Mn-TiO2It urges
Agent is denoted as catalyst sample 9#。
10 synthesis gas C of embodiment2Oxidiferous reaction evaluating
Respectively to catalyst sample D1#、1#~9#In synthesis gas C2Reactivity worth in oxycompound is evaluated, tool
Steps are as follows for body:
Above-mentioned catalyst is before use, H in the reactor2(GHSV=5000h-1) in-situ reducing activation, condition are carried out in stream
Are as follows: normal pressure, 5 DEG C/min is from room temperature to 450 DEG C, and holding 3 hours in H2It is cooled to reaction temperature in stream and switches to synthesis
Gas.CO hydrogenation conditions are as follows: 280 DEG C, 5.0Mpa, H2/ CO=2, GHSV=5000h-1.Reaction end gas after cold-trap absorbs,
Gas-phase product carries out on-line analysis, and chromatographic apparatus is Agilent 3000A Micro GC, molecular sieve, Plot Q, Al2O3And OV-1
Four capillary columns, TCD detector.Liquid product off-line analysis, FFAP capillary chromatographic column, fid detector.Internal standard method point
Analysis, isobutanol alcohol are internal standard compound.Acetic acid is quantitative by acid base titration.
Reaction result is summarised in table 1.
The support type rhodium base catalyst sample being prepared it can be seen from data in table 1 using herein described method
1#~9#CO conversion ratio and the selectivity of ethyl alcohol, acetaldehyde, acetic acid is much higher than and is prepared using typical impregnation method
Sample D1#.Wherein, sample 2#(2nmRh/Mn-SiO2) and sample 3#(3.5nmRh/Mn-SiO2) CO high conversion rate in other samples
Product, C2Oxidiferous selectivity is also relatively high, illustrates Ru nanoparticle in the range of 2~5nm, the support type rhodium base is urged
Agent is in synthesis gas C2Reactivity worth in oxycompound is preferable.
Table 1:CO adds reaction result of the hydrogen on embodiment catalyst
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of support type rhodium base catalyst, which is characterized in that the support type rhodium base catalyst includes main active component and load
Body；
Wherein, the main active component contains rhodium element and manganese element, and rhodium element and manganese element are in support type rhodium base catalyst
Weight percentage be 0.01~20.0wt%；
The carrier is selected from least one of silica, aluminium oxide, titanium oxide.
2. support type rhodium base catalyst according to claim 1, which is characterized in that the specific surface area of the silica is 5
~400m2/ g, average pore size are 1~200nm；
The specific surface area of the aluminium oxide is 20~300m2/ g, average pore size are 5~100nm；
The specific surface area of the titanium oxide is 20~100m2/ g, average pore size are 10~100nm.
3. support type rhodium base catalyst according to claim 1, which is characterized in that rhodium element exists in the main active component
Weight percentage in support type rhodium base catalyst is 0.1~10.0wt%；
Preferably, in the main active component weight percentage of the rhodium element in support type rhodium base catalyst be 0.5~
5.0wt%.
4. support type rhodium base catalyst according to claim 1, which is characterized in that manganese element exists in the main active component
Weight percentage in support type rhodium base catalyst is 0.1~10.0wt%；
Preferably, in the main active component weight percentage of the manganese element in support type rhodium base catalyst be 0.5~
5.0wt%.
5. support type rhodium base catalyst according to claim 1, which is characterized in that in the main active component rhodium element with
The form of rhodium nanoparticle exists；
The average grain diameter D of the rhodium nanoparticle50A certain value between 1~20nm, (D90-D10)/D50≤1.0；
Preferably, the average grain diameter D of the rhodium nanoparticle50A certain value between 1~10nm, (D90-D10)/D50≤0.7；
It is further preferred that the average grain diameter D of the rhodium nanoparticle50A certain value between 1~7.5nm, (D90-D10)/D50
≤0.5。
6. the method for preparing support type rhodium base catalyst described in any one of claim 1 to 5, which is characterized in that include at least
Following steps:
A) Mn is carried on carrier using infusion process, obtains the carrier of load Mn；
B) rhodium nanoparticle is obtained；
C) use infusion process that rhodium nanometer particle load on the carrier of load Mn, is obtained the support type rhodium base catalyst.
7. according to the method described in claim 6, it is characterized in that, the preparation method of rhodium nanoparticles includes following in step b)
Step:
Solution I containing organic rhodium complex is mixed with the solution II for closing borine containing organic amine, is reacted in 190~240 DEG C
No less than 2 hours to get arrive the rhodium nanoparticles.
8. according to the method described in claim 6, it is characterized in that, the preparation method of rhodium nanoparticles includes following in step b)
Step:
Acetylacetone,2,4-pentanedione rhodium is dissolved in oleyl amine and obtains solution I；
Tert-butylamine borine is dissolved in oleyl amine and obtains solution II；
Solution I is heated to 190~240 DEG C and solution I is added in solution II, after reacting 2~6h, is cooled to 40~80 DEG C, warp
Washing, separation after to get arrive the rhodium nanoparticle.
9. a kind of synthesis gas C2Oxidiferous method, which is characterized in that by support type described in any one of claim 1 to 5
At least one in rhodium base catalyst, the support type rhodium base catalyst being prepared according to any one of claim 6 to 8 the method
Kind, with synthesis gas haptoreaction, prepares C after reduction pretreatment2Oxycompound；
The C2Oxycompound is selected from least one of ethyl alcohol, acetaldehyde, acetic acid.
10. according to the method described in claim 9, it is characterized in that, the condition of the reduction pretreatment are as follows: at 400~500 DEG C
At a temperature of using containing H2Gas to 2~6h of the support type rhodium base catalyst prereduction；
The described and catalytic condition of synthesis gas are as follows: reaction temperature is 280~350 DEG C, and reaction pressure is 3.0~5.0MPa,
The volume space velocity of synthesis gas is 1500~1000h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810255401.XA CN110354852B (en) | 2018-03-26 | 2018-03-26 | Supported rhodium-based catalyst, preparation method thereof and method for preparing C from synthesis gas2Use in oxygenates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810255401.XA CN110354852B (en) | 2018-03-26 | 2018-03-26 | Supported rhodium-based catalyst, preparation method thereof and method for preparing C from synthesis gas2Use in oxygenates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110354852A true CN110354852A (en) | 2019-10-22 |
| CN110354852B CN110354852B (en) | 2021-05-25 |
Family
ID=68213011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810255401.XA Active CN110354852B (en) | 2018-03-26 | 2018-03-26 | Supported rhodium-based catalyst, preparation method thereof and method for preparing C from synthesis gas2Use in oxygenates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110354852B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101450A (en) * | 1977-05-09 | 1978-07-18 | Celanese Corporation | Catalyst for production of acetic acid |
| CN1354043A (en) * | 2000-11-22 | 2002-06-19 | 中国科学院大连化学物理研究所 | Lawrencium base catalyst for preparing C2 oxygen-contained compound by using synthetic gas |
| CN102029173A (en) * | 2009-09-25 | 2011-04-27 | 中国科学院化学研究所 | Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas |
| CN102218329A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas |
| CN102784660A (en) * | 2012-07-19 | 2012-11-21 | 上海师范大学 | Supported metal palladium catalyst, its preparation and its application |
| CN104307512A (en) * | 2014-10-14 | 2015-01-28 | 武汉大学苏州研究院 | Supported palladium catalyst and preparation method and application thereof |
-
2018
- 2018-03-26 CN CN201810255401.XA patent/CN110354852B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101450A (en) * | 1977-05-09 | 1978-07-18 | Celanese Corporation | Catalyst for production of acetic acid |
| CN1354043A (en) * | 2000-11-22 | 2002-06-19 | 中国科学院大连化学物理研究所 | Lawrencium base catalyst for preparing C2 oxygen-contained compound by using synthetic gas |
| CN102029173A (en) * | 2009-09-25 | 2011-04-27 | 中国科学院化学研究所 | Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas |
| CN102218329A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas |
| CN102784660A (en) * | 2012-07-19 | 2012-11-21 | 上海师范大学 | Supported metal palladium catalyst, its preparation and its application |
| CN104307512A (en) * | 2014-10-14 | 2015-01-28 | 武汉大学苏州研究院 | Supported palladium catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 俞俊: "一氧化碳加氢合成C2含氧化合物铑基催化剂的研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110354852B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102781574B (en) | Fischer-tropsch synthesis catalyst, manufacturing method therefor, and hydrocarbon manufacturing method | |
| CN112871198B (en) | Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof | |
| Zhan et al. | Green synthesis of Au/TS-1 catalysts via two novel modes and their surprising performance for propylene epoxidation | |
| CN1970143A (en) | Method for preparing high-activity hydrogenation catalyst nano Ru/C | |
| CN108654638B (en) | Core-shell cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN105618095B (en) | Porous nano carborundum load platinum catalyst and preparation and the application in alpha, beta-unsaturated aldehyde selective hydrogenation reaction | |
| CN111215084A (en) | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof | |
| CN109420515A (en) | A kind of preparation method of high-dispersion loading type metallic catalyst | |
| CN107199036A (en) | Supporting Pt and WOx a kind of catalyst and preparation method thereof | |
| CN110652983A (en) | Catalyst for hydrogenolysis of polyhydric alcohol and process for producing 1, 3-propanediol using the same | |
| CN107952495B (en) | Regeneration method and application of Fischer-Tropsch synthesis catalyst | |
| CN105727953A (en) | Fischer Tropsch synthesis catalyst for preparing heavy hydrocarbon product through synthesis gas and preparation method of catalyst | |
| CN112108145A (en) | Alumina-supported iridium cluster catalyst and preparation and application thereof | |
| CN113058596B (en) | High-stability CO 2 Preparation and application of catalyst for preparing ethanol by hydrogenation | |
| CN110420669A (en) | Cu cluster preparation method and catalysis CO2React purposes | |
| CN105903466A (en) | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN110935481A (en) | Catalyst for selective hydrogenolysis of aromatic ether bond, preparation and application thereof | |
| CN112774690B (en) | Supported single-atom noble metal catalyst and preparation method and application thereof | |
| CN1247305C (en) | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed | |
| CN110354852A (en) | A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound | |
| Toukoniitty et al. | Continuous Enantioselective Hydrogenation of Ethylbenzoylformate over Pt/Al 2 O 3 Catalyst: Bed Dilution Effects and Cinchonidine Adsorption Study | |
| CN113508104A (en) | Process for the selective oxidation of glycerol | |
| CN104248953A (en) | Catalyst for preparation of ethanol by acetate hydrogenation and preparation method thereof | |
| WO2017193696A1 (en) | Catalyst, preparation method therefor and application thereof in preparation of syngas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |