CN1044601A - Catalyst - Google Patents
Catalyst Download PDFInfo
- Publication number
- CN1044601A CN1044601A CN90100983A CN90100983A CN1044601A CN 1044601 A CN1044601 A CN 1044601A CN 90100983 A CN90100983 A CN 90100983A CN 90100983 A CN90100983 A CN 90100983A CN 1044601 A CN1044601 A CN 1044601A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- prereduction
- temperature
- hydrogen
- group viii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008676 import Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- 230000002427 irreversible effect Effects 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
By the preliminary treatment before the prereduction, can make the support type group VIII metallic catalyst that improves active reduction.When carrying out preliminary treatment, the catalyst precarsor of load group VIII metal under the temperature that is lower than the prereduction temperature (general about 140 ℃) that can detect catalyst prereduction reaction, is soaked in the reducing atmosphere.This catalyst can exemplify out ruthenium/oxysome Al catalysts, it is characterized in that, and is long-pending at least about 45M with the group VIII metallic surface that the carbon monoxide absorption method is measured
2/ g is carried on the group VIII metal on the catalyst.
Description
The invention relates to catalyst, particularly about the group VIII metal catalyst.
According to the present invention, a kind of catalyst of group VIII metal of the reduction that contains load is provided, this catalyst comprises carrier and up to the group VIII metal of about 10wt%, it is characterized in that the group VIII metal surface area is at least about 45m
2/ g is carried on the group VIII metal on the catalyst, adopts the carbon monoxide determination of adsorption method.
When measuring the group VIII metal surface area, suppose that an occupied area of carbon monoxide molecule that is adsorbed is 16.8 * 10
-20m
2(16.8
2).
The feature of catalyst of the present invention is that the group VIII metal surface area is at least about 45m
2/ g is carried on the group VIII metal on the catalyst, and different with it is, handles the catalyst that the load of making behind the same catalyst precarsor has group VIII metal with conventional prereduction method, and the surface area of the group VIII metal of its exposure is starkly lower than about 45m
2The group VIII metal of/g load.
The document record shows that the catalytic activity of the hydrogenation catalyst of group VIII metal depends on the metallic that is reduced after prereduction is handled.Draw thus, activity of such catalysts is more or less directly relevant with the surface area of reduction back metal exposed.The surface area that is the reduced metal exposure is big more, and activity of such catalysts is just high more.Under extreme case, group VIII metal loads on the carrier with the single metal atomic form.
In the preferred form of catalyst of the present invention, the group VIII metal on the catalyst all is to exist with the reduced metal particulate forms basically.
Catalyst precarsor contains a kind of oxidation thing or salt and a kind of carrier of group VIII metal.With the salt solution impregnated carrier of group VIII metal, carry out roasting in case of necessity again, can make suitable precursor.Suitably also can adopt coprecipitation under the situation.The whole bag of tricks of the suitable catalyst precarsor of preparation is that Preparation of Catalyst field those of ordinary skill is known.It is believed that this class catalyst precarsor is that reducible shape crystal by group VIII metal is evenly distributed on the carrier substantially and constitutes.The various conditions that the size of these crystal grain generally adopts when depending on the preparation catalyst precarsor.It is believed that these crystal grain are more little, metallic surface is long-pending in the reducing catalyst just can be big more.So the method for preparing catalyst precarsor will influence the size of the final surface area of group VIII metal on the reducing catalyst.The method of reducing of catalyst system therefor also will produce this influence.
Group VIII metal can be preparation any in those metals commonly used during loaded catalyst, used those metals when especially preparing the hydrogenation catalyst of group VIII metal.Concrete example comprises platinum, palladium, ruthenium, rhodium.
Can utilize any suitable carrier, as aluminium oxide, silica one aluminium oxide, thorium oxide, carborundum, titanium oxide, chromium oxide, zirconia or carbon.The content range of group VIII metal in the catalyst precarsor, the 0.01wt% that generally is about catalyst precarsor weight are typically up to about 5wt%, 0.5wt% according to appointment up to 10wt%.
Typical catalyst precarsor is the powder that particle diameter is not more than about 100 μ m.Available routine techniques and commonly used adhesive, lubricant are processed into the shape of any conventional catalyst with such powder, as garden cylindricality particle, and annular, saddle types etc. are so that can use in the fixed-bed operation process.
The present invention also provides a kind of method for preparing catalyst.In the method, the catalyst precarsor that load is had group VIII metal can obviously detect under the prereduction temperature of catalyst prereduction process in hydrogeneous atmosphere, and heating is carried out prereduction and handled.The feature of this method is, before carrying out above-mentioned prereduction processing, elder generation under poor hydrogen condition, places the atmosphere that contains a large amount of inert gases and micro-hydrogen with catalyst precarsor fully, and under the temperature that is lower than above-mentioned prereduction temperature, carry out the preceding preliminary treatment of prereduction.In above-mentioned atmosphere, being heated to the prereduction temperature from room temperature is comparatively easily.All to keep poor hydrogen condition in the whole pre-treatment step before the prereduction in the methods of the invention, even catalyst precarsor always is in the state that lacks hydrogen, so that the rate of reduction of group VIII metal oxide or salt is subjected to the available quantitative limitation of hydrogen on the catalyst precarsor surface.Like this, just the rate of reduction of group VIII metal can be become controlled rate.This step with the difference of the step that the producer of this catalyst precarsor of preparation is recommended usually is: being heated to about 140 ℃ whole process from room temperature all is that the gaseous mixture existence that only contains micro-reducibility gas is therein carried out down, and conventional method then is to heat in 100% nitrogen atmosphere.The mechanism of making the active catalyst of group VIII metal from catalyst precarsor still imperfectly understands, but it seems that this mechanism comprises the oxide of a part of group VIII metal to major general's carrier or the reduction process that salt is reduced into corresponding group VIII metal.Though when temperature is lower than the prereduction temperature when (typical prereduction temperature is about 140 ℃), as if detect less than the generation that responds between catalyst precarsor and the hydrogen-containing gas, but in fact truly have very a spot of group VIII metal oxide or salt to be reduced, the nucleation that occurs the group VIII metal atom thus, this does not see with simple microscope, just as in the camera during exposure, the nucleation of the silver atoms that occurs not seeing under the simple microscope is the same.Though with the naked eye do not see the sub-image on the exposed plate, the flushing process through conventional makes film contact with reducing agent, just can make this sub-image become visible video picture.Equally, it is contemplated that, pre-treatment step among the present invention before the prereduction can cause " sub-image " to generate, this sub-image is by the group VIII metal atomic building of the coring of can't see under a large amount of simple microscopes, the metallic atom of these nucleation can grow up to many tiny metallic particles respectively, thereby guarantees that the group VIII metal on the group VIII metal catalyst that make, the process reduction correspondingly has sizable exposed surface area.On the other hand, if adopt traditional prereduction technology, promptly in the presence of hydrogen-containing gas, preheat rapidly under about 180 ℃ or the higher temperature, perhaps earlier catalyst precarsor is preheated in inert atmosphere at least about 180 ℃, contact with hydrogen-containing gas again, then the initial nuclear crystalline phase that forms of group VIII metal atom is when few, and brilliant group VIII metal oxide and the salt source point that is reduced into metal that has served as subsequently of this nuclear, so group VIII metal may form sizable crystal grain, therefore cause the exposed surface area of metal less, and the lower result of the activity of catalyst in hydrogenation reaction.
By adopting suitable temperature-temporal mode, regulate the composition of the entrance and exit place gas of pre-former conversion zone, can guarantee the pre-treatment step that prereduction is preceding or soak into the related any reaction of gas step, always under minimum as far as possible temperature, carry out, and before temperature obviously raises again, react fully as far as possible.In addition, utilize any heat that exothermic reaction produced in the preprocessing process before hydrogen-containing gas is taken away prereduction, to reduce pyrolytic damage as far as possible to catalyst.
The inventive method comprises that gas soaks into step.No liquid exists in this step, and gas fully is penetrated in the catalyst precarsor, reaches osmotic equilibrium simultaneously.
Gas in the preferred process of the present invention soaks in the step, under the temperature between room temperature (15 ℃-25 ℃ according to appointment are typically about 20 ℃) and the prereduction temperature (typical about 180 ℃), the group VIII metal catalyst precarsor is remained in the hydrogeneous atmosphere.Gas soaks into the temperature that step begins can be lower than room temperature, as 0 ℃ or lower.In this step, except that inert gas such as nitrogen, helium or argon gas, only contain the hydrogen of trace in the typical hydrogeneous atmosphere, generally be not higher than about 1V%, 0.5V% preferably, or still less.Soak in the step at this gas, though preferably fully in hydrogeneous atmosphere, catalyst precarsor is heated to the prereduction temperature from room temperature, but also can in inert atmosphere, begin heating, under room temperature (if the words that begin to heat from the temperature that is lower than room temperature) or higher relatively temperature (40 ℃ according to appointment-Yue 50 ℃), introduce hydrogeneous atmosphere then.But, an essential feature of this method is, in the gas process of osmosis, temperature is more near the prereduction temperature, and it is important more to make the catalyst precarsor that always contacts with hydrogeneous atmosphere still be under the poor hydrogen condition this point.
Gas at selection method of the present invention soaks in the step, and catalyst precarsor is at suitable gas hourly space velocity 500hr according to appointment
-1-Yue 6000hr
-1Hydrogen-containing gas streams in, under the controlled condition, from room temperature (20 ℃ according to appointment) begin the heating.Hydrogen-containing gas preferably includes micro-hydrogen (typically being lower than about 1V%) and a large amount of one or more inert gases such as the gaseous mixture of nitrogen, argon, neon, methane, ethane, butane or two or more mixed inert gas.In a particularly preferred method, reducing gases is micro-hydrogen (preferably less than about 0.5V%, 0.2V% according to appointment) and a large amount of nitrogen, preferably the gaseous mixture of the nitrogen of anaerobic basically.
The gas of the inventive method soaks into step can be operated under normal pressure or decompression, operates but be preferably under the elevated pressure that about 1-20 clings to or better about 2-10 clings to.
Gas soaks in the step, and required hydrogen partial pressure is not higher than about 0.01 crust, can be between about 0.0005 Ba-Yue 0.005 crust.
In the method that the present invention selects the superior especially, catalyst precarsor in containing the reducing atmosphere of micro-hydrogen, is heated to about 140 ℃ from room temperature.Catalyst precarsor is preheated about 140 ℃ process from room temperature, be preferably under the control speed and carry out; General this preheats step and proceeds to about 48hr or longer time, 24hr according to appointment from about 12hr.In the gas soak process, temperature can raise by the speed of substantial linear, or raises by stage by stage form roughly, as every about 5 ℃-10 ℃ be one-level, temperature is kept substantial constant after a period of time therebetween, continue intensification again.From about 140 ℃-180 ℃ heating process, heating can be followed any curve of temperature-time, as long as can control the rate of heat addition, make catalyst precarsor in whole process, remain under the reducing condition, keep substantially the same each other the getting final product of gas composition of the import and the outlet of prereduction conversion zone simultaneously.Preferred heating mode is to make temperature by the substantial linear mode, is elevated to about 180 ℃ from about 140 ℃.In a kind of step, employing be mode of heating progressively, for simplicity, the temperature interval is about 10 ℃, and before each step heating, among and after, carefully detect the gas composition that the prereduction conversion zone is imported and exported.Under typical operating condition, from about 140 ℃-180 ℃ temperature-rise period, heating rate is that about 1 ℃/hr is to about 15 ℃/hr, 10 ℃/hr according to appointment.
From about 140 ℃-180 ℃ heating process, gas flow rate generally is equivalent to gas hourly space velocity (measuring) under 0 ℃, 1 bar pressure, be about 400hr above-mentioned
-1-Yue 6000hr
-1Or higher, 3000hr according to appointment
-1
The composition of hydrogen-containing gas depends on operating pressure, and stagnation pressure is high more, and the highest admissible hydrogen concentration is low more.Otherwise stagnation pressure is low more, and the hydrogen concentration in the reducing gases can be high more.Under the general operating condition according to qualifications, H
2Concentration is about 0.01%(V/V)-Yue 1%(V/V), 0.2%(V/V according to appointment),
In case catalyst precarsor reaches about 180 ℃ final temperature value, hydrogen partial pressure just raises gradually.But, in the catalyst activation process in this stage, must note regulating the composition that the prereduction conversion zone is imported and exported gas, make the gas composition of two places substantially the same in whole process.In case of necessity, also can further be heated to again up to about 210 ℃ or higher temperature.
When catalyst precarsor reaches the prereduction temperature, should not have obviously excessive hydrogen, so that any infringement that the heat out of control that reduces to produce in the catalyst prereduction step by heat release as far as possible causes catalyst.Guarantee that this point is very important.
The prereduction catalyst of preparation is described according to the present invention, very responsive to oxidation, this may be since the group VIII metal particle had certain again due to the oxidation.Therefore, after the prereduction catalyst makes, preferably place inert gas or hydrogeneous atmosphere.
Catalyst of the present invention can be used in a kind of various reactions of its at least a hydrogenation products of unsaturated organic compound hydrogenation preparing.
Further specify the present invention with example below.
Example 1 and 2
Two batches of spherolitic PG 88/10 0.5%Ru/ aluminium oxide catalyst precursors of 3.0 * 3.0mm (can from Davy McKee(London) are obtained, address: Limited of Davy House, 68 Hammersmith Road, London, W14 8YW) sample is respectively charged into reative cell.Catalyst precarsor is through careful weighing, and weight is respectively 2.5g between the 2.6g.Under the room temperature (20 ℃), at outlet pressure 4.45 crust, gas flow rate 200l/hr(0 ℃, 1 crust is measured down) condition under, fed oxygenless nitrogen 30 minutes to reative cell.In nitrogen stream, add hydrogen then, make when keeping overall flow rate constant, contain 0.2% hydrogen in the nitrogen stream.Reaction chamber temperature is raised to 140 ℃ gradually with 5 ℃/hr speed, and the nitrogen stream flow velocity that maintenance contains 0.2% hydrogen is constant.Utilize thermal conductivity constantly to regulate the gas of import and export.In the time of about 24hr, gradually amounts of hydrogen is brought up to 1% slightly successively.To be detected when having hydrogen to be absorbed again, with 15 ℃/hr speed temperature is raised to 160 ℃, and till keeping this temperature when the import and export gas composition is identical, this shows that the absorption of hydrogen process stops.In 2hr, catalyst temperature is brought up to 180 ℃.Catalyst temperature is remained on 180 ℃, and the various conditions of system are remained unchanged reaches 18hr simultaneously, hydrogen content is brought up to 100% gradually therebetween.When air-flow is replaced into 100% hydrogen stream, temperature is brought up to 200 ℃, and keep this temperature 1hr, catalyst can come into operation afterwards.
After above-mentioned reduction processing, place the anaerobic helium flow to be chilled to 20 ℃ catalyst.Make ruthenium surface and reaction of carbon monoxide after the reduction, measure the surface area of ruthenium by this.Suppose that the surface that a carbon monoxide molecule occupies is 16.8 * 10
-20m
2(16.8A
2), by continuously carbon monoxide is injected helium flow when detecting less than further reaction till, can measure degree that reaction carries out and the number that is adsorbed on the lip-deep carbon monoxide molecule of ruthenium.Can calculate the exposed surface area of metal Ru in the reducing catalyst thus.
It is long-pending to list absorbing state and corresponding Ru metallic surface below.
Table 1
| Real column number | The CO amount of reaction (molecule/g) | The Ru surface area | |
| m 2/ g catalyst | m 2/gRu | ||
| 1 2 | 1.78×10 191.43×10 16 | 0.287 0.240 | 57.4 48.0 |
Comparative example A and B
With with example 1 and 2 used identical catalyst precarsors, compare example experiment in the following manner.
Be respectively charged into the spherolite sample of 3ml catalyst precarsor again to each reative cell.At outlet pressure 4.45 crust, gas hourly space velocity 3000hr
-1Condition under, in 1.5hr, in 100% hydrogen stream, catalyst precarsor is heated to 210 ℃, and under this temperature, kept 30 minutes, characterize then.
Utilize the reaction of carbon monoxide technology of example 1 and 2, obtain following result.
Table 2
| The contrast column number | The CO amount of reaction (molecule/g) | The Ru surface area | |
| m 2/ g catalyst | m 2/g Ru | ||
| A B | 7.9×10 171.03×10 18 | 0.134 0.173 | 26.8 34.6 |
Can find out after the The above results that relatively adopt the gas of example 1 and 2 to soak into step, the surface area that can make is much higher than the surface area of its corresponding ruthenium in comparative example A and B.
Example 3-6
In these examples, the catalyst sample example 1 of packing into separately is reactor used, follow these steps to operation:
1, at room temperature, gas hourly space velocity 1800hr
-1, make oxygenless nitrogen under 4.45 bar pressures, pass through reactor, all keep above-mentioned gas hourly space velocity value in the whole experiment.
2, under 20 ℃, make to contain 0.2%H
2Nitrogen stream reach 24hr by catalyst.
3, by 5 ℃/min speed temperature is raised to 140 ℃, regulates the import and export gas composition simultaneously.
4, when the import and export gas composition is identical, in 24hr, with H
2Content slowly brings up to 1%.
5, by 0.25 ℃/min speed temperature is brought up to 160 ℃, and keep 4hr under this temperature, after this, import and export gas reaches same composition.
6, in the 4hr, with H
2Content slowly brings up to 5%, again it is kept 4hr.
7, with the speed of 0.25 ℃/min temperature is brought up to 180 ℃, keep 4hr again.
8, temperature is brought up to 200 ℃ again with the speed of 0.25 ℃/min, then, in 6-8hr, made H
2Content is increased to 100% gradually.
9, with 100%H
2Under 200 ℃, keep 8hr at least.
10, under 200 ℃, use 100%N
2Purging system, and at N
2Be chilled to 25 ℃ under the flushing, to carry out following absorption research.
Experimental technique below utilizing characterizes the ability that these catalyst sample irreversible chemicals adsorb carbon monoxide with the dynamic method of stream of pulses:
11, under 25 ℃, with pure helium with gas hourly space velocity 1800hr
-1Purging system.
12, the 500 μ l pulse of helium stream that will contain 5% carbon monoxide injects air flow, measures the CO content of discharging from reactor with thermal conductivity detector.As calculated, containing peak area that the 500 μ l calibration pulse streams of 5%CO obtain and absorption back discharges the difference of the peak area of gas and is CO amount in the adsorbed stream of pulses of catalyst sample.
13, repeat above-mentioned steps 12, till obviously not having the adsorption reaction generation again.According to the result who obtains, can determine the total amount of the CO of Irreversible Adsorption.
Because the dynamic pulse flow method of absorption can only draw the amount of the carbon monoxide of Irreversible Adsorption, in order to determine the metallic area of catalyst, the total amount of measuring the carbon monoxide that is adsorbed is very important.This point can be passed through the radiotracer method, at 25 ℃, promptly with used uniform temp of dynamic pulse flow method and static conditions under, measure
14The adsorption isotherm of C carbon monoxide is realized.Purge catalyst sample with helium flow, and measure the reduction value that causes surperficial counting rate because of deduction reversible adsorption material, can determine the amount of that part of CO of Irreversible Adsorption.The amount of the CO of Irreversible Adsorption is 50 ± 2% of the total adsorption capacity of catalyst in the sample of all detections.
The absolute magnitude of the carbon monoxide of the Irreversible Adsorption of measuring with above-mentioned dynamic pulse flow method can be determined the area of the metal that exposes in the reducing catalyst.To each sample, suppose that wherein the carbon monoxide of Irreversible Adsorption is 50% of a catalyst absorption carbon monoxide total capacity, suppose that carbon monoxide is adsorbed by linear mode, this point obtains affirming of far-infrared spectrum, and supposes that the area of the carbon monoxide molecule that is adsorbed is 16.8 * 10
-20m
2(16.8
2), can calculate the gross area of metal.
Four parts of PG, the 88/10 0.5%Ru/ aluminium oxide catalyst precursor that example 3-6 adopts is taken from two different batch of materials.This two batch of material is labeled as sample A and B.Example 3 and 5 two parts of used catalyst precarsors are respectively unreduced sample A and B, and the two parts of catalyst precarsors in addition in the example 4 and 6 are respectively sample A and the B that has also contacted air through conventional prereduction technical finesse subsequently again.The result lists in the following table 3.
The sample A of example 3,4 is except that handling both differences of this point through prereduction, and all the other are all identical.The result of reference examples 3,4 can find out that the method for pre-treatment step only has very important influence to the exposed surface area of metal on the reducing catalyst before the enforcement prereduction.Traditional prereduction process has obviously caused
Certain aggtegation of reproducibility ruthenium crystal grain on the catalyst precarsor, and the present invention can not cause this clustering phenomena.Can be observed similar result from example 5 and 6.Example 5 and 6 is except that the catalyst of example 6 has been handled through conventional prereduction, and the both is identical.(catalyst that example 3 and 5 illustrates wherein belongs to the scope of the invention, and example 4 and 6 but is not).
Comparative Examples C-G
In these Comparative Examples, make other catalyst samples A and B in the reactor of example 1, stand the prereduction of routine techniques and handle.This prereduction is handled and is made of the following step:
1,25 ℃ and 1800hr
-1Gas hourly space velocity under, make hydrogen under 4.45 bar pressures, pass through reactor.
2, the speed with 10 ℃/min is raised to 200 ℃ with temperature, keeps above-mentioned hydrogen flow rate simultaneously.
3, catalyst is placed under the above-mentioned condition 11hr at least.
4, at 200 ℃, use 100%N
2Purge, and it is chilled to 25 ℃, keep this N simultaneously
2Stream passes through.
5, the used CO determination of adsorption method metal surface area of use-case 3-6.
Below table 4 list the gained result.
Can notice, different with the result of routine 3-6, adopt these Comparative Examples of conventional prereduction technology, there is not obviously difference between the metal surface area of measuring of not going back raw sample and prereduction sample, and the inventive method shown in the use-case 3-6, the metal surface area on the raw catalyst precursor approximately is two times of prereduction sample metal surface area.
Example 7
Adopt the conventional method of routine 3-6, handle following catalyst sample, obtain similar good result:
The 0.1%Pt/ aluminium oxide
The 0.1%Rh/ aluminium oxide
The 0.1%Pd/ aluminium oxide
0.1%Ru/ carbon
0.1%Pt/ carbon
0.1%Rh/ carbon
0.1%Pd/ carbon
Claims (17)
1, a kind of contain modification, through the support type group VIII metal catalyst of reduction, comprise carrier and a kind of group VIII metal up to about 10Wt%, it is characterized in that the VII family metallic surface that goes out with the carbon monoxide determination of adsorption method amasss at least about 45m
2/ g is carried on the VII family metal on the catalyst.
2, according to the catalyst of claim 1, wherein contained basically whole group VIII metals are that the particulate forms with the group VIII metal that is reduced exists.
3, according to the catalyst of claim 1 or 2, wherein group VIII metal comprises ruthenium.
4, according to each described catalyst among the claim 1-4, wherein carrier is an aluminium oxide.
5, a kind of method for preparing catalyst, wherein under the prereduction temperature that can obviously detect catalyst prereduction reaction, in the hydrogeneous atmosphere, catalyst precarsor heating carrying out prereduction to the load group VIII metal is handled, it is characterized in that, carrying out before above-mentioned prereduction handles, under the temperature that is lower than above-mentioned prereduction treatment temperature and contain a large amount of inert gases and have only in the hydrogen-depleted gas atmosphere of micro-hydrogen, above-mentioned catalyst precarsor is being immersed in the preliminary treatment of carrying out in the above-mentioned atmosphere before the prereduction.
6, according to the method for claim 5, wherein in hydrogeneous atmosphere, be heated to described prereduction temperature from room temperature.
7, according to the method for claim 5 or 6, about 140 ℃ of prereduction temperature wherein.
8, according to each described method among the claim 5-7, wherein with precursor under the temperature between room temperature and the prereduction temperature, remain in the hydrogeneous atmosphere.
9, according to each described method among the claim 5-8, catalyst precarsor wherein begins heating from room temperature in the hydrogen-containing gas streams under controlled conditions, and this hydrogen-containing gas streams comprises the gaseous mixture that has only micro-hydrogen and a large amount of one or more inert gases.
10, according to the method for claim 9, hydrogen-containing gas wherein is the no oxygen gas mixture of micro-hydrogen and a large amount of nitrogen.
11, according to each described method among the claim 5-10, gas wherein soaks into step to carry out under about 2 crust-10 bar pressures.
12, according to each described method among the claim 5-11, gas wherein soaks in the step, and the dividing potential drop of hydrogen is about 0.0005 crust-0.005 crust.
13, according to each described method among the claim 5-12, wherein with catalyst precarsor in containing the atmosphere of micro-hydrogen, control the rate of heat addition be heated to about 140 ℃ from room temperature.
14, according to each described method among the claim 5-13, wherein pressing temperature-time curve heats catalyst precarsor about 140 ℃-Yue 180 ℃ of scopes, its rate of heat addition is wanted to make catalyst precarsor in whole process, remain under the reducing condition, and the import and export gas composition of prereduction conversion zone is substantially the same.
15, according to each described method among the claim 5-14, wherein with catalyst precarsor when about 120 ℃ are heated to about 170 ℃, it is about 400hr that gas flow rate will be equivalent to gas hourly space velocity (at 0 ℃, measuring under the 1 crust condition)
-1-Yue 6000hr
-1
16, according to each described method among the claim 5-15, catalyst precarsor wherein contains ruthenium.
17, according to each described method among the claim 5-16, carrier wherein is an aluminium oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898901977A GB8901977D0 (en) | 1989-01-30 | 1989-01-30 | Catalyst |
| GB8901977.2 | 1989-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1044601A true CN1044601A (en) | 1990-08-15 |
Family
ID=10650821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100983A Pending CN1044601A (en) | 1989-01-30 | 1990-01-26 | Catalyst |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0455661A1 (en) |
| JP (1) | JPH04503027A (en) |
| KR (1) | KR910700098A (en) |
| CN (1) | CN1044601A (en) |
| CA (1) | CA2045664A1 (en) |
| GB (1) | GB8901977D0 (en) |
| WO (1) | WO1990008592A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4221139A1 (en) * | 1992-06-27 | 1994-01-05 | Huels Chemische Werke Ag | Catalyst and process for the selective hydrogenation of unsaturated compounds and process for the preparation of the catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1448859A (en) * | 1973-12-05 | 1976-09-08 | British Petroleum Co | Reduction of platinum group metal catalysts |
| US4028227A (en) * | 1974-09-24 | 1977-06-07 | American Cyanamid Company | Hydrotreating of petroleum residuum using shaped catalyst particles of small diameter pores |
| NL8201696A (en) * | 1982-04-23 | 1983-11-16 | Unilever Nv | METHOD FOR PREPARING METHANATION CATALYSTS |
| US4503274A (en) * | 1983-08-08 | 1985-03-05 | Uop Inc. | Ruthenium hydrogenation catalyst with increased activity |
-
1989
- 1989-01-30 GB GB898901977A patent/GB8901977D0/en active Pending
-
1990
- 1990-01-26 CN CN90100983A patent/CN1044601A/en active Pending
- 1990-01-29 KR KR1019900702185A patent/KR910700098A/en not_active Application Discontinuation
- 1990-01-29 EP EP90901841A patent/EP0455661A1/en not_active Withdrawn
- 1990-01-29 CA CA002045664A patent/CA2045664A1/en not_active Abandoned
- 1990-01-29 JP JP2502187A patent/JPH04503027A/en active Pending
- 1990-01-29 WO PCT/GB1990/000130 patent/WO1990008592A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990008592A1 (en) | 1990-08-09 |
| EP0455661A1 (en) | 1991-11-13 |
| GB8901977D0 (en) | 1989-03-22 |
| KR910700098A (en) | 1991-03-13 |
| CA2045664A1 (en) | 1990-07-31 |
| JPH04503027A (en) | 1992-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2832336B2 (en) | Gold ultrafine particle-immobilized substance and method for producing the same | |
| US20100217052A1 (en) | Catalyst For The Selective Hydrogenation Of Acetylenic Hydrocarbons And Method For Producing Said Catalyst | |
| CN111989156B (en) | Shell catalyst based on platinum-sulphur, production and use in hydrocarbon dehydrogenation | |
| Sancier | Hydrogen migration on alumina/palladium catalysts for benzene hydrogenation | |
| CN1221653A (en) | Process for preparing shell-type catalyst | |
| EP4223412A1 (en) | Ammonia decomposition catalyst | |
| Holstein et al. | Hydrogenolysis of carbon and its catalysis by platinum | |
| Kweskin et al. | High-pressure adsorption of ethylene on cubic Pt nanoparticles and Pt (100) single crystals probed by in situ sum frequency generation vibrational spectroscopy | |
| Kim et al. | Easily Scalable Shell‐Structured Copper Catalyst with High Activity and Durability for Carbon Dioxide Hydrogenation | |
| CN1044601A (en) | Catalyst | |
| CN112452355B (en) | Preparation method of carbon material catalyst applied to preparation of styrene | |
| CN1695805A (en) | Catalyst carried by Nano carbon fiber in use for refining terephthalic acid through hydrogen added | |
| CN1103394A (en) | Process for converting 1,2-dichloropropane to propylene | |
| Wells et al. | Butene isomerization catalyzed by supported metals in the absence of molecular hydrogen | |
| Bogel-Łukasik et al. | Pt-and Pd-catalysed limonene hydrogenation in high-density carbon dioxide | |
| Wong et al. | Hydrogenolysis and hydrogenation of hydrocarbons on supported Rh–Ir bimetallic catalysts | |
| DE102005001290A1 (en) | Apparatus and method for removing carbon monoxide from a hydrogen-containing gas stream | |
| Othman et al. | On the characteristics and hydrogen adsorption properties of a Pd/γ-Al2O3 prepared by sol–gel method | |
| RU2385857C1 (en) | Method of purifying styrene from phenylacetylene impurities | |
| US2079404A (en) | Catalyst preparation | |
| Takahashi et al. | Hydrogenation of cyclohexene and benzene over an amorphous pd‐zr alloy | |
| Ma et al. | PVP-Pt nanoclusters supported zeolite catalysts for converting methane to higher hydrocarbon at low temperature | |
| Szummer et al. | Effect of hydrogenation under high pressure on the structure and catalytic properties of Cu–Zr amorphous alloys | |
| RU2497587C2 (en) | Method of making membrane catalyst and method of hydrocarbon dehydration using obtained catalyst | |
| CN114073987B (en) | Catalyst for eliminating formaldehyde through storage-oxidation tandem connection and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |