CN1104950C - Ruthenium catalyst using alumina as carrier - Google Patents
Ruthenium catalyst using alumina as carrier Download PDFInfo
- Publication number
- CN1104950C CN1104950C CN97182511A CN97182511A CN1104950C CN 1104950 C CN1104950 C CN 1104950C CN 97182511 A CN97182511 A CN 97182511A CN 97182511 A CN97182511 A CN 97182511A CN 1104950 C CN1104950 C CN 1104950C
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- catalyst
- component
- alumina
- earth metal
- 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.)
- Expired - Fee Related
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 110
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 claims description 86
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 36
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- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 25
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 24
- 238000007598 dipping method Methods 0.000 claims description 22
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
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- 229910052753 mercury Inorganic materials 0.000 description 3
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- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- KLUYKAPZRJJIKT-UHFFFAOYSA-N lutetium Chemical compound [Lu][Lu] KLUYKAPZRJJIKT-UHFFFAOYSA-N 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BBMRFTLCEAZQEQ-UHFFFAOYSA-N oxalic acid;oxozirconium Chemical compound [Zr]=O.OC(=O)C(O)=O BBMRFTLCEAZQEQ-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Chemical class CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical group Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
A process for preparing an alumina-supported ruthenium catalyst having at least one ruthenium component supported on porous alpha-alumina, wherein the catalyst has a specific surface area 1) Adjusted to 7-50 m2Specific surface area of porous alpha-alumina2) With the above surface area (S)1) Ratio of (i.e. S)2/S1) Adjusting the peak value to 3-5, and forming a microporous structure with a peak value of 5-1000. The support component of the catalyst has good crushing strength and activity per unit weight of ruthenium, and the heat resistance of the catalyst is sufficient to maintain high activity even under conditions of high temperature occurring during calcination or reaction.
Description
Background of invention
Invention field
The present invention relates to be carried on the ruthenium catalyst on the aluminium oxide.More specifically, the present invention relates to be carried on the ruthenium of ruthenium catalyst on the aluminium oxide-wherein or similar components by the Alpha-alumina porous material carry-these catalyst are advantageously used in the various hydrogen production methods, be particularly useful for utilizing vapour reforming production to be used to produce synthetic gas, be suitable for the reducing gas that direct reduction iron making is used, the light hydrocarbons of town gas and hydrogen etc. and oxygenatedchemicals.The ruthenium catalyst that is carried on the aluminium oxide of the present invention also is advantageously used in the reformer (being used to produce hydrogen) that is included in the fuel cell.
Technical background
At the conventional vapour reforming of the light hydrocarbons that utilizes catalyst or similarly in the method, used usually by the catalyst carrier transition metal that for example gama-alumina the carried catalyst made of nickel for example.
In this vapour reforming, in order to save engineering cost and cost of use, heat flux tries hard to make its rising, and the ratio (S/C) of steam/carbon tries hard to make its decline.Under such operating condition, carbon is deposited on the catalyst easily, thereby causes pressure reduction to increase on pipeline.Therefore, the blocking pipe of catalyst meeting sometimes makes and continues reaction generation difficulty.So, suddenly needing a kind of catalyst, its quantity that goes up the carbon of generation is compared with the quantity that catalyst reached of routine and has been subjected to great inhibition when using this catalyst, demonstrates high catalytic activity simultaneously.
The ruthenium that contains that is carried on the aluminium oxide has become as the ruthenium catalyst of catalyst component and makes the people interested, and this is because it can suppress the activity that carbon deposition and having has thereon increased.Since be carried on the shown good catalytic performance of ruthenium catalyst on the aluminium oxide for its in use even the high activity under the ratio condition of low steam/carbon and suppress the ability that carbon deposits and confirmed, Japanese patent application publication No. 5-220397 discloses and has wherein also included the ruthenium catalyst that is loaded on the aluminium oxide, is wherein carried by the aluminium oxide that contains alkali earth metal aluminate in the zirconia and the ruthenium component of precursor zirconia sol.
, the ruthenium catalyst that is carried on the aluminium oxide that is disclosed in the above-mentioned reference has following problem, and promptly under low steam/carbon ratio (S/C) 2 or the littler the condition of reorganization and under less than 680 ℃ hot conditions, its activity is not enough.Also have,, make the catalyst that contains ruthenium become useful, except requiring to guarantee to have the gratifying catalytic performance, also require to suppress the content of ruthenium, so that reduce the cost of catalyst industrial because ruthenium belongs to the high noble metal of valency.In addition, in view of steam reforming reaction all at high temperature carries out, so seek to develop not only have high active but also be the catalyst of heat resistanceheat resistant.
From preventing to be caused by air pollution the viewpoint of environmental disruption, it is interesting that hydrogen fuel has become, this be because its can gasoline replacing etc. as alternative energy resources.For example, by fuel battery energy hydrogen fuel is reformatted into electric energy.Usually, the hydrogen as parent material is produced by hydro carbons or oxygenatedchemicals by vapour reforming.Especially, oxygenatedchemicals for example methyl alcohol and methyl ether has begun to be required fuel as transportation power source (electric motor car) recently, replaces being used for habitually the hydro carbons such as town gas and liquid propane gas of fuel cell.As the catalyst of using for reforming oxygenated compounds, used by the catalyst carrier ruthenium of supported on alumina (or being impregnated into) for example, nickel, or metalloid.
Typical fuel cell comprises a reactor that is used to reform usually.In recent years, the reforming reaction still that is many concentric hollow cylinder shapes is popularized, many catalyst layers have wherein been disposed to form cylindrical shell, so that make the overall fuel cell miniaturization and improve its performance (Japanese patent application publication No. 3-122001 and 60-264303).
In the reforming reaction still of the above-mentioned type, place a burner in the housing central authorities of innermost layer, and many layer catalyst layers round this burner arrangement, make the area of heating surface reach maximum and the size that reduces reactor whereby.So, beginning the operation moment and the shut-down operation moment at reactor, the temperature of the inboard of catalyst layer has different greatly with the temperature in this catalyst layer outside.This temperature difference causes on the circumferencial direction of each housing producing strain owing to thermal expansion is different, then a kind of compression force is arranged on catalyst layer, under pressure, this compression stress catalyst of may crushing.After this catalyst was crushed, powder just produced, and blocking catalyst layer and downstream line, thereby may operation be ended because of flow resistance raises.
As a kind of measure that prevents that catalyst is broken under pressure, " fuel associating magazine " the 68th volume the 3rd phase (1989) P.236～243 on a kind of ruthenium catalyst that is carried on the aluminium oxide is disclosed, ruthenium wherein is as catalyst, and Alpha-alumina is as catalyst carrier.
But, because the ruthenium catalyst that is carried on the aluminium oxide that is disclosed on the above-mentioned magazine has used the Alpha-alumina of using the method preparation of roasting gama-alumina down at 1300 ℃, this molded Alpha-alumina is used in many housings type reforming reaction still, its crushing strength that has is not enough, because the demanding crushing strength of aforesaid reaction vessel.In addition, because ruthenium is carried by the Alpha-alumina that obtains by the roasting gama-alumina, so the catalyst that generates has little of 6.6m
2The specific area of/g, so, even with highly active ruthenium when the active component, ruthenium can not be dispersed on the carrier fully and carrier in, therefore, only can obtain active not enough catalyst.In addition, usually after sufficiently high roasting temperature is prepared Alpha-alumina with the method that increases crushing strength, the Alpha-alumina that generates is a very fine and close structure, normally inappropriate as catalyst carrier, because it does not have the micropore of sub-micron or smaller szie, in addition, even after it is moulded to catalyst carrier, it also only has little specific area.In other words, when the catalyst carrier of being made by alpha-aluminium oxide is used activity component impregnation, active component is dispersed on this carrier satisfactorily and carrier in necessary specific area be not enough, therefore, even increase the quantity of catalytic component, can not obtain enough activity.
As the above, Japanese patent publication 5-220397 similarly discloses a kind of ruthenium catalyst that is carried on the aluminium oxide, and the zirconia and the ruthenium component that wherein derive from the precursor zirconium dioxide are carried by the aluminium oxide that comprises alkali earth metal aluminate.
But, consider that zirconia sol used in above-mentioned publication is to occur with 100 or bigger particle form, so be considered to grow up to particle for big from the zirconia that wherein obtains.In addition,, alkali earth metal aluminate occurs, so its particle also is considered to grow up to and is bulky grain because being grains.So estimating that this catalyst has has reduced specific area and the not enough shortcoming of catalytic activity.
Summary of the invention
In view of the above problems, finished the present invention, purpose of the present invention just provides a kind of ruthenium catalyst-wherein a kind of Woelm Alumina material that is carried on the aluminium oxide, because its good hear resistance and crushing strength, as catalyst is useful, this Woelm Alumina material activity component impregnation, and ruthenium-it has many outstanding features: in the ruthenium of per unit weight, has very good activity, especially reforming activity; Has good heat resistance to guarantee in the reaction at high temperature high activity being arranged; And have long-term service life.
Above-mentioned purpose can realize that this catalyst comprises at least a ruthenium component by the carrying of Woelm Alumina material, the specific area (S that this catalyst has by the ruthenium catalyst that is carried on the aluminium oxide
1) be 8～50m
2/ g.
In preference pattern of the present invention, the above-mentioned specific area S that is carried on the ruthenium catalyst on the aluminium oxide
1Surface area (S with porous Alpha-alumina material
2) ratio (S
1/ S
2) be 3-50.
In another preference pattern of the present invention, the ruthenium catalyst that is carried on the aluminium oxide has one to have the micropore vertical section that at least one peak value drops on 5～1000 .
In another preference pattern of the present invention, porous Alpha-alumina material floods with at least a ruthenium component and a kind of zirconium component, and corresponding amount (content) is such, by being converted into elements ruthenium, the former accounts for 0.05～5wt%, by being converted into zirconia, the latter accounts for 0.05～20wt%, and the two all is to calculate according to the weight of porous Alpha-alumina material.
In another preference pattern of the present invention, porous Alpha-alumina material is with at least a ruthenium component, a kind of zirconium component, with a kind of alkaline-earth metal or alkene earth metal component dipping, their content separately is, by being converted into elements ruthenium, ruthenium ingredients constitute 0.05～5wt%, by being converted into zirconia, zirconium ingredients constitute 0.05～20wt%, by the corresponding oxide of being converted into alkaline-earth metal or rare earth metal, they have accounted for 0.5～20wt%, and wherein all percentage all are to calculate with respect to the weight of porous Alpha-alumina material.
Also have in another preference pattern of the present invention, porous Alpha-alumina material is with at least a ruthenium component, a kind of zirconium component, a kind of alkaline-earth metal or rare earth metal component, with a kind of cobalt component dipping, their content separately is, by being converted into elements ruthenium, ruthenium ingredients constitute 0.05～5wt% is by being converted into zirconia, zirconium ingredients constitute 0.05～20wt%, by the corresponding oxide of being converted into alkaline-earth metal or rare earth metal, they occupy 0.5～20wt%, and wherein all percentage all are to calculate with respect to the weight of porous Alpha-alumina material, and the cobalt component is that 0.01-30 introduces with the mol ratio Co/Ru of cobalt (Co) and ruthenium (Ru) then.
In addition, provide the catalyst that a kind of steam reforming reaction that is suitable for hydro carbons is used, utilize the above-mentioned ruthenium catalyst that is carried on the aluminium oxide exactly.
Implement optimal mode of the present invention
The various embodiments that are carried on the ruthenium catalyst on the aluminium oxide of the present invention are narrated below.
I. porous Alpha-alumina material
In the present invention, porous Alpha-alumina material is used as alumina support.Can be used for this porous Alpha-alumina material of the present invention and be selected from its composition of routine and the above-mentioned material that performance has been adjusted and controlled by following method, promptly introduce additive, preliminary treatment, or select appropriate preparation method.For example, can make porous Alpha-alumina material stand chemical treatment, for example acid treatment, alkali treatment, or ion-exchange treatment are so that adjust its acidity whereby; Heating or roasting are so that be adjusted at lip-deep water content of this alumina material or OH content; Or multiple measure, so that control the size and distribution and relevant surface area of micropore whereby.
Shape and size to porous Alpha-alumina material of the present invention are not done special restriction.Can process through granulating as the parent material alpha-alumina powder, compression process, injection moulding, or stand other suitable processing method to form powder, particle, globule, small column, piller, or Raschig rings.All these all be applicable to of the present invention.In addition, have special construction for example global shape and the carrier matrix that makes by the material that chemical reaction is inertia, can spray the raw material alpha-alumina powder, to form catalyst carrier of the present invention whereby.
The collateral security catalyst has enough specific areas, in course of reaction, the low pressure loss is arranged in catalyst layer, with the viewpoint consideration that improves the thermal conductivity of reacting fluid, in these catalyst carriers, preferred catalyst carrier is through granulating processing or is molded into bead, globule, piller, or the porous Alpha-alumina material of Raschig rings and adopt to give special construction for example overall structure coat the coating material that the method for Alpha-alumina forms.In the material of these types, consider high compression strength, preferred especially bead, globule, Raschig rings and the integral carriers matrix that applies.
The physical characteristic and the manufacture method of the porous Alpha-alumina material that adopts among the present invention will be told about below.
1. the physical characteristic of porous Alpha-alumina material
Preferred in the present invention the porous Alpha-alumina material that uses with following physical characteristic.
(1) micropore volume
The micropore volume of preferred porous Alpha-alumina material is generally 0.05～0.5cc/g, more preferably 0.1～0.4cc/g, most preferably 0.1～0.3cc/g.If volume is less than 0.05cc/g, the amount of liquid that Alpha-alumina absorbs very little, that is, it can not absorb the following dipping solution that contains active catalyst component fully.Therefore, may introduce the catalytic component deficiency of carrier.Otherwise, greater than the micropore volume of 0.5cc/g-this shows that Alpha-alumina is an incomplete sintering-may cause crushing strength not high.
(2) mean pore size
The pore size of preferred porous Alpha-alumina material is generally.0.01～100 μ m are preferably 0.05～50 μ m, more preferably 0.1～10 μ m.When this size surpassed 100 μ m, when implementing the step of following usefulness active catalyst component impregnated carrier, this carrier can not be possessed dipping solution, so, not only require the repeated impregnations operation, and operating efficiency is poor.Otherwise when this size during less than 0.01 μ m, the parent material hydrocarbon can not easily be diffused in course of reaction in the micropore in the catalyst.In this case, can not obtain and the suitable catalytic activity of active catalyst component quantity of carrying by porous Alpha-alumina material.
(3) specific area
In order to make the catalyst of making by the method for active component being introduced porous Alpha-alumina material increase its specific area, want preferably itself to have the Alpha-alumina material of high surface area,, generally speaking, mechanical strength is tending towards along with the increase of Alpha-alumina specific area descending.In the present invention, Alpha-alumina carries surface area own and is generally 0.05m
2/ g or bigger, preferred 0.1～3m
2/ g, and more preferably 0.2～1m
2/ g.
(4) crushing strength
The crushing strength of porous Alpha-alumina material is generally 20kgf or bigger, and preferred 20～200kgf, and more preferably 40～100kgf record according to the crushing strength measurement mechanism of Kiya.When the support strength that uses as 20kgf or more hour, this catalyst is used for course of reaction, especially in the process that reactor is heated or cooled, may be broken, otherwise, even when its intensity surpasses 100kgf, also must not obtain the technical advantage suitable with this intensity.
(5) degree of crystallinity
The degree of crystallinity of porous Alpha-alumina material is generally 70% or bigger, and preferred 90% or bigger, more preferably 95% or bigger.When the degree of crystallinity of porous Alpha-alumina material less than 70% the time, this porous material itself or demonstrate low crushing strength from the catalyst prod that wherein makes, thus when it is used for course of reaction, might in reactor, produce attritive powder.When porous Alpha-alumina material is made X-ray diffraction analysis, by " the highest peak value intensity that compound caused except Alpha-alumina " (I
B) and " by the highest peak value intensity that Alpha-alumina caused " (I
A) ratio I
B/ I
ABe preferably 0.1 or littler, more preferably 0.01 or littler, compound wherein also comprises gama-alumina, η-aluminium oxide, and βYang Hualv except Alpha-alumina.When peak strength than (I
B/ I
A) greater than 0.1 o'clock, its catalytic activity of catalyst of being made by this porous Alpha-alumina material was low often.
2. make the method for porous Alpha-alumina material (1) initial powder material
Porous Alpha-alumina material of the present invention then is the method manufacturing of sintering by the granulating processing or the processing that is shaped then, and just obtaining parent material is alpha-alumina powder.
Preferred 0.01～100 μ m of the particle diameter of initial powder material, more preferably 0.05～50 μ m, and 0.1～10 μ m most preferably.
When particle diameter during, always can not obtain desired pore size of catalyst or micropore volume, otherwise when particle diameter surpassed 100 μ m, crystal grain was not easy sintering, so can not obtain having the porous material of sufficient mechanical strength less than 0.01 μ m.
(2) additive
Often multiple additives is mixed mutually with alpha-alumina powder, so that accelerate sintering reaction or form porous.Some embodiment of additive comprise inorganic additive, for example clay mineral and waterglass; And organic additive, for example different types of starch crystal grain (corn, wheat, dogtooth violet plant lily, and potato), polyethylene, ethylene glycol, PVA (polyvinyl alcohol), MC (methylcellulose), CMC (carboxymethyl cellulose), glycerine, sorbierite, urea, propylene, emulsion class and wax class.Some examples of clay mineral comprise kaolin, bentonite and frog order clay.
When additive is inorganic material, preferred 0.01～100 μ m of the particle diameter of this additive, more preferably 0.05～50 μ m, and 0.1～10 μ m most preferably.
The introducing amount of these additives is 100 weight portions in Alpha-alumina, preferably less than 50 weight portions, is more preferably less than 20 weight portions.
(3) die pressing
Porous Alpha-alumina material of the present invention can utilize the starting powder material that contains multiple additives to make by different mould pressing methods usually.Unrestricted to mould pressing method, some examples of these class methods comprise die pressing, rolling granulation, wet method injection molding, CIP method of molding, granulation and powder injection molding.On the other hand, porous Alpha-alumina material of the present invention can make by spraying an integrally-built method of making separately.
Moulded product is classification in addition as required, and roasting in addition in 1100～1600 ℃ gas burner for example, so that final products are provided, and porous Alpha-alumina material promptly of the present invention.
II. metal component (by the component of alpha-alumina supports carrying)
In the present invention, the ruthenium component-it has confirmed to demonstrate at least high activity-be introduced in the above-mentioned alpha-alumina supports in reforming reaction.Consider and strengthen catalytic activity and guarantee long service life, the industrial multicomponent system catalyst that preferably also contains other component described below.Introduce consumption-ruthenium that above-mentioned " other component " can also reduce ruthenium because of be noble metal expensive-so as to reducing the unit cost of making catalyst.
(1) two-component system (ruthenium and zirconium)
In preference pattern of the present invention, provide a kind of catalyst that contains ruthenium component and zirconium component as two kinds of major metal components.
When these two kinds of metal components were introduced into alumina support, zirconia was to occur with very thin particle form, so the catalyst of generation has has expanded surface area significantly.Therefore, this catalyst demonstrates high activity and good hear resistance.
Can suitably select the consumption of corresponding metal component according to related factors and condition, related factors and condition comprise the characteristic (for example kind, surface area etc.) or the Application of Catalyst (i.e. the type of the reaction of Guan Xining and character) of carrier.For example, the amount of used ruthenium component among the present invention for the weight of carrier, is generally 0.05～5wt%, preferred 0.05～2wt%, more preferably 0.1～2wt% (calculating according to metal Ru).The consumption of zirconium component is determined according to vehicle weight, is generally 0.05～20wt%, preferred 0.1～15wt%, and more preferably 1.0～15wt% (calculating according to zirconia).
(2) three-component system (ruthenium, zirconium and alkaline-earth metal or rare earth metal)
In the present invention, except ruthenium component and zirconium component, one or more kind components that are selected from alkaline earth metal component and rare earth metal component can also be incorporated in the carrier.Some examples of alkaline earth metal component and rare earth metal component comprise beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and/lutetium (Lu).In above these elements, in view of magnesium has remarkable effect to the hear resistance that improves the zirconium component, so preferably magnesium.The total amount of these components is generally 0.5～20wt%, preferred 0.5～15wt%, and more preferably 1～10wt%, these all are to calculate according to the corresponding oxide of alkaline earth metal component or rare earth metal component.
Get magnesium component among alkaline earth metal component and the rare earth metal component as typical example, will below the catalyst of having introduced the magnesium component be described.
In this case, ruthenium, zirconium and magnesium are introduced as three kinds of key components.
Have these three kinds of metal components to be introduced in the catalyst of alumina support therein, zirconium and magnesium are to occur with the form of very thin zirconia crystal grain and magnesia crystal grain respectively.These two kinds of matter interactions have suppressed the formation and the grain growth of crystal.Therefore, the surface area of this catalyst has remarkable increase, forms high catalytic activity and good hear resistance whereby.
Consider above-mentioned condition, the amount of the metal component that the present invention is used can suitably be selected.For example, for vehicle weight, the consumption of ruthenium component is generally 0.05～5wt%, preferred 0.05～2wt%, and more preferably 0.1～2wt% calculates according to metal Ru.The consumption of zirconium component is generally 0.05～20wt%, preferred 0.1～15wt%, and more preferably 1.0～15wt% calculates according to zirconia.The consumption of magnesium component is generally 0.5～20wt%, and preferred 0.5～15wt% calculates according to magnesia.When the consumption of magnesium component during less than 0.5wt%, this catalytic activity may be low.
Be included in the magnesium component in the catalyst and the mol ratio of zirconium component, Mg/Zr is generally 0.1～10, and is preferred 0.5～5, and more preferably 1～2, and ratio Mg/Zr wherein is equivalent to the mol ratio of magnesium atom (Mg) and zirconium atom (Zr).When mol ratio Mg/Zr less than 0.1 the time, the inhibitory action that the component of introducing reduces surface area is performance and increase stable on heating effect and may become not enough fully not.On the other hand, even when mol ratio surpasses 10, stable on heating improvement neither be suitable.
In the present invention, in order further to improve activity of such catalysts,, preferably introduce the zirconium component as following described.
(3) four component system (ruthenium, zirconium, alkaline-earth metal or rare earth metal, and cobalt)
In the present invention, the cobalt component is an optional components, and its consumption is such, and the mol ratio (Co/Ru) of cobalt (Co) and ruthenium (Ru) is generally 0.01～30, and is preferred 0.1～30, more preferably 0.1～10.When mol ratio less than 0.01 the time, cobalt content reduces, therefore, improving active predictive role can not reach.On the other hand, when mol ratio surpassed 30, relative ruthenium content reduced.In this case, the ruthenium steam reformation type catalyst that contains that is applicable to hydro carbons is difficult to keep its high activity.In addition, even under the operating condition of low steam/carbon ratio, stop the effect of carbon deposition to be obstructed.
III. the specific area of catalyst
In the present invention, can access the catalyst that specific area has remarkable increase by method with specific metal component dipping porous Alpha-alumina material.This is because these corresponding metal components are to occur with very thin crystal grain form, but they can not block the micropore of porous Alpha-alumina material again.
In addition, catalyst of the present invention not only demonstrates high catalytic activity, and demonstrates high mechanical strength and hear resistance, and these all are features of Alpha-alumina.
The specific area of catalyst of the present invention is generally 7～50m
2/ g, preferred 8～20m
2/ g, more preferably 8～15m
2/ g.Specific area is less than 7m
2/ g will never provide gratifying catalytic activity, because these metal components must not be dispersed on the carrier widely or in the carrier.On the other hand, specific area surpasses 50m
2/ g represents that pore size is too little, is diffused in the micropore so can hinder original material.In this case, increasing specific area may be inoperative.
Specific area (the S of catalyst of the present invention
1) with ratio S as the specific area of the porous Alpha-alumina material of carrier
1/ S
2Preferred 3 or bigger, more preferably 5～50, especially preferred 10～30.When this ratio less than 3 the time, can not obtain to be enough to demonstrate the catalyst of the required specific area that possesses of gratifying catalytic activity.
IV. the peak value that distributes of catalyst micropore
Catalyst of the present invention has micropore.It is such that the micropore of this catalyst distributes, and has at least a peak value to drop in 5～1000 , preferred 10～100 .These micropores are to be formed by the component that is carried on the Woelm Alumina material.The distribution of micropore is to utilize this amount to estimate according to nitrogen in the adsorbance that the absorption-desorption properties under the different pressures calculates nitrogen.On the micro-pore diameter distribution map, in scope, there is not peak value less than 1000 , show not form satisfied micropore: specific area is not enough, and therefore, active component does not distribute on carrier fully, causes reactivity to descend., when when the scope less than 5 has peak value, these micropores are excessively little again and can hinder reactive material enters into micropore, causes playing the effect that improves activity.
V. the metal group public affairs are incorporated in the porous Alpha-alumina material 1. the method for Yin Ruing
In the present invention, do not do special restriction for the method that metal component is incorporated in the porous Alpha-alumina material.For example, above-mentioned porous Alpha-alumina material can flood with the solution that contains following component, this solution contains at least a or more kinds of ruthenium compounds, with optional one or more kind zirconium compounds that contain, the compound that one or more kinds are selected from alkaline earth metal compound and rare earth compound (for example, one or more plant magnesium compound), also can further choose any one kind of them or more kinds of cobalt compound.In such method, ruthenium component and some optional components, for example zirconium component, alkaline earth metal component, rare earth metal component and cobalt component, they are coated on the surface of porous Alpha-alumina material equably, or are introduced in the micropore of porous Alpha-alumina material, and evenly distribute.In addition, even after the preliminary treatment of having carried out such as roasting at high temperature and this quasi-representative of reduction, ruthenium component and zirconia component still can keep homogeneously dispersed state, thereby are easy to form high performance ruthenium-containing catalyst.
(1) solution
For containing the solution of metal compound of using in the above-mentioned introducing method, by adding acids additives etc., its pH preferably is adjusted to 3 or littler, more preferably 1.5 or littler.If the pH of this solution surpasses 3, deposition or cohesion formation gel can take place in one or more contained kind compounds in the solution, and therefore, this (a bit) metal component will never be homogeneously dispersed state and remain on the carrier.On the contrary, when pH is 3 or more hour, can infer that this ruthenium compound and zirconium compounds etc. react, and have formed complexing shape compound, when being shaped, it also is introduced into, and forms the catalyst that catalytic activity has further improvement with activation.
In addition, except that containing ruthenium component and zirconium component, the catalyst that also contains the additive that is alkaline-earth metal or rare earth metal component form has the highly stable specific area of heat, this heat endurance after fuse the reaction or at high temperature still can keep in the course of reaction.Therefore, this catalyst demonstrates long-term hear resistance.
(2) solvent
The solvent used to above-mentioned solution has no particular limits, and can use to dissolve at least a ruthenium compound and optional compound i.e. zirconium compounds, any solution of alkaline earth metal component or rare earth metal component and cobalt compound.Some examples of this solvent comprise water, water-based solvent, and organic solvent, for example pure and mild ether.Preferred water or water-based solvent among them are because above-claimed cpd has high solubility therein.
(3) raw material of metal component
Kind and shape as the compound of the parent material of metal component are not subjected to special restriction, can be dissolved in the above-mentioned solvent as long as this changes the Yu thing.Some examples of initial compounds are as follows.
(3-1) ruthenium compound
The halide that some examples of available ruthenium compound comprise ruthenium among the present invention is ruthenium trichloride for example, and the ruthenium halide Barbiturates is like as hexachloro-potassium ruthenate; The ruthenic acid salt is four oxygen potassium ruthenates for example; Ruthenium tetroxide; Ammino closes for example six ammino ruthenium terchorides of salt; With cyano group complexing salt six cyano group potassium ruthenates for example.It in addition, in solvent, have the compound of low solubility also to can be used as raw material in the present invention, as long as can or become soluble under the situation of acidity or alkali cpd coexistence by acidity or alkali compounds additives.For example, though the oxide of ruthenium (for example ruthenium sesquioxide), the hydroxide of ruthenium, with oxyhalide of ruthenium etc., be about under 7 the condition all water insoluble or water-soluble slightly at pH, but they all can be used for the present invention, because having under the acids situation that for example hydrochloric acid adds, they all become soluble.The compound of these rutheniums can use separately or two or more uses that combine.
In these original ruthenium compounds, preferred especially ruthenium trichloride, industrial because it is widely used for, and on market, bought easily.
(3-2) zirconium compounds
Some embodiment of available zirconium compounds comprise halide for example zirconium chloride or halid incomplete hydrolysate among the present invention; Oxyhalide is zirconyl chloride (basic zirconium chloride) for example; The oxyacid salt is zirconium oxysulfate for example, zirconium nitrate, and zirconyl nitrate; Zirconic acid salt for example four oxygen base potassium zirconiums and hexafluoro closes sodium zirconate; Organic acid salt or organic coordination compounds be the acetic acid zirconium for example, zirconium oxyacetate, oxalic acid oxygen zirconium and four oxalic acid base potassium zirconiums; The alcoholates of zirconium; The hydroxide of zirconium; With zirconium complexing salt.These compounds are dissolvable in water those compounds in the solvent except comprising under normal operation (promptly under the situation that does not have acid), also comprise those compounds that are dissolvable in water in the acid flux material that comprises sour for example hydrochloric acid or acid compound.
In these zirconium compounds, Ren Xuan oxychloride especially.Some examples of this oxychloride comprise by ZrOCl
2NH
2O or ZrO (OH) ClnH
2The hydrate of O representative and commercially availabie group water solution.Basic zirconium chloride is considered to form the compound of certain the similar complex compound that contains ruthenium.These zirconium compounds can use separately or two or more uses that combine.
(3-3) alkaline earth metal compound and rare earth compound
The Nitrates that available alkaline earth metal compound and rare earth compound comprise alkaline-earth metal and rare earth metal among the present invention, chloride, acetic acid salt, and Oxalates; And the alkoxide cpd of these metals.Their some examples comprise for example magnesium nitrate of Nitrates, calcium nitrate, strontium nitrate, lanthanum nitrate, and cerous nitrate; Chloride is magnesium chloride for example, calcium chloride, strontium chloride, lanthanum chloride, and cerium chloride; The acetic acid salt is magnesium acetate and calcium acetate for example; Oxalates is magnesium oxalate for example, calcium oxalate and strontium oxalate; With alkoxide cpd magnesium methoxide for example, magnesium ethylate, calcium methoxide, and calcium ethoxide.These compounds comprise by adding for example hydrochloric acid of acids, acid compound, or alcohol for example becomes after the methyl alcohol and is dissolvable in water those compounds of solvent.In these compounds, consider that Nitrates and chloride have high solubility, so preferential the use.These compounds can use separately or two or more uses that combine.
(3-4) cobalt compound
Available cobalt compound comprises some compounds that are dissolvable in water in the specific solvent among the present invention, and by soluble those compounds that become after adding acid for example the method for hydrochloric acid or acid compound adjusting the pH of solvent.Their some embodiment comprise cobalt nitrate, alkaline cobalt nitrate, cobaltous dichloride and their compound.In these compounds, in view of the Nitrates of cobalt with chloride has high solubility and preferential the use, and especially preferentially use cobalt nitrate.These cobalt compounds can use separately or two or more uses that combine.
(4) preparation of solution (4-1) step of preparation solution
When the above-mentioned solution of preparation, for interpolation, mix, or dissolve corresponding component, comprise solvent, ruthenium compound, zirconium compounds, alkaline earth metal compound or rare earth compound, order and method that cobalt compound and acid ground are adopted have no particular limits.For example, specific component can be simultaneously or ground be added in the solvent or add in the sour acid solution.On the other hand, some solution that contain respective components of preparation can be mixed separately.Can prepare the solution that contains the part component earlier, can then remaining component be added wherein then.Though solution is preferably measured near room temperature,, when requiring accelerate dissolution, can be heated to about 80 ℃.
Inorganic acid (for example hydrochloric acid, sulfuric acid, and nitric acid) and organic acid (for example acetate and oxalic acid) can be used for improving the solubility of original chemical in solvent and adjust the pH of solution.
(4-2) amount of the metal component of Yin Ruing
When also using together as the zirconium dioxide of catalytic component and ruthenium, represent the ratio of zirconium compounds and ruthenium compound so that zirconium (Zr) and rubbing of ruthenium (Ru) are happy than (Zr/Ru), this ratio is 100 or littler, and is preferred 1～50, more preferably 2～20.When mol ratio Zr/Ru less than 1 the time, the dispersity possible deviation of ruthenium component on carrier perhaps can not keep the ruthenium component near the zirconium component.So think that such reason is the compound that the part ruthenium compound can not form similar complex compound.Otherwise, when mol ratio Zr/Ru surpasses 100, the ruthenium component on the carrier and the dispersity on the carrier no longer improve, and what is worse, be covered with the zirconium component on the ruthenium component because a spot of ruthenium component is exposed to carrier surface, thereby reduced catalytic activity.In addition, the good characteristic of porous Alpha-alumina material may be damaged.
When alkaline earth metal compound or rare earth compound combine when using, be generally 0.01-10 with the mol ratio of alkaline-earth metal or rare earth metal (M) and the ratio M/Zr representative of zirconium (Zr), preferred 0.05～5, more preferably 0.1～5.When mol ratio (M/Zr) less than 0.01 the time, the alkaline earth metal compound of interpolation or rare earth compound can not play the effect of expection.In other words, may descend when this catalyst is exposed to high temperature its specific area of following time in reaction or roasting process, the hear resistance of carrier can not increase.On the other hand, even mol ratio M/Zr surpasses 10, stable on heating improvement can not be suitable.
When cobalt compound was used to be used in combination, cobalt compound was generally 0.01～30 by the mol ratio (Co/Ru) of cobalt (Co) and ruthenium (Ru), and is preferred 0.1～30, and more preferably 0.1～10 condition is used.When this mol ratio when simultaneously the cobalt constituent content is low less than 0.01, improving active predictive role may not reach, otherwise if this mol ratio surpasses 30, relative ruthenium content reduces.In this case, be applicable to that the ruthenium steam reforming catalyst that contains of hydro carbons is difficult to keep its high activity, in addition, under the operating condition of low steam/carbon ratio, the effect that suppresses the carbon deposition may reduce.
(4-3) every kind of component concentrations
The quantity (concentration) that is dissolved in every kind of compound in the above-mentioned solution is had no particular limits.The concentration of ruthenium compound is generally elected 0.001mol/l or bigger as, and preferred 0.01～1mol/l, and more preferably 0.1～0.5mol/l are fixed according to the molar concentration of ruthenium.
Above-mentioned solution can comprise zirconium compounds except comprising basic ruthenium compound, alkaline-earth metal or rare earth compound, and cobalt compound, solubility is regulated component, and other component that needs, only otherwise can hinder effectiveness of the present invention just.
(4-4) uniform dissolution
For every kind of compound is dissolved in the solvent equably, the pH of this solution should adjust to 3 or littler, preferably adjusts to 1.5 or littler.If pH surpasses 3, hydrolysis takes place and forms hydroxide class colloidal sol or gel in zirconium component easily.Colloidal sol that generates or gel are considered to have any problem when forming the compound of above-mentioned similar complex compound with the ruthenium component, so, add the dispersiveness that the zirconium component can not cause improving the ruthenium component.
2. flood (1) kind of method
Utilize the solution of preparation as stated above,, each metal component can be carried on the porous Alpha-alumina material by the dipping method of routine.Some examples of this method comprise various dipping methods (heating dipping, normal temperature dipping, vacuum impregnation, atmospheric pressure dipping, dry infusion process, the filling perforation method, their any combination etc.), water seaoning, light soaks method, moisture absorption method, gunite, coating process and their combined method.Any method all can adopt, as long as it can make solution and porous Alpha-alumina material contact, so that this (a bit) metal component is carried on the Alpha-alumina material.Though require to carry out at least in order single-steeping in the present invention, drying, and baking operation, each step can repeat arbitrarily for several times.(2) ratio of porous Alpha-alumina material and dipping solution
The ratio of alumina support and dipping solution can be according to aim parameter, the concentration of metallic compound in the employed aqueous solution of the active metal component that is carried, the micropore volume of the type of dipping method and employed porous Alpha-alumina material and specific area wait to determine.
(3) operating condition
Operating condition to impregnating process has no particular limits.Generally speaking, impregnating process be in environment temperature to about 80 ℃ a certain temperature, preferably under room temperature or a certain temperature, and under atmospheric pressure or decompression (owing to bleeding), carry out near room temperature.
(4) drying behind the dipping
Porous Alpha-alumina material is done dry the processing thereupon after with above-mentioned metal component dipping.Drying condition is had no particular limits.Drying was generally carried out under 50～150 ℃ one hour or longer, preferably carried out under 100～120 ℃ 12 hours or longer.Under the air drying regime, approximately to carry out whole diel (24 hours).A large amount of moisture potential evaporations, this depends on the type of the dipping method that is adopted, so very Gan Zao Woelm Alumina material is getable.Under these circumstances, do not need to carry out separately drying steps.
(5) dried roasting
By top described drying porous Alpha-alumina material carry out roasting subsequently to form catalyst.Roasting generally be in air or moving air under 400～800 ℃, preferably under 450～800 ℃, more preferably under 450～600 ℃, carried out about 1～24 hour.In calcination atmosphere, can all or part ofly make oxygen-containing gas for example purity oxygen and oxygen-enriched air.
By the catalyst prod that roasting obtains, wherein carrying ruthenium component and optional zirconium component, alkaline earth metal compound or rare earth compound and cobalt component, and these components of being carried generally are the form of oxide or complex oxide.These compositions are reciprocally approaching, and are carried in the porous Alpha-alumina material with the high degree of dispersion state.
(6) preliminary treatment
The catalyst of Huo Deing can directly be used as catalyst or be used as a component in specific catalytic reaction like this, perhaps can adopt the appropriate pretreatment method to make its activation, is used for catalytic reaction subsequently.Preliminary treatment can utilize usual way to carry out.For example, the ruthenium component for example can be utilized the reducing agent of hydrogen and so on to reduce its metal Ru that is reformatted into high degree of dispersion is used for reaction.
The method of reducing that utilizes hydrogen generally is to carry out under 500～850 ℃, till no longer having observed hydrogen consumption.
VI. the steam reforming reaction of hydro carbons and oxygenatedchemicals
Having under the situation that is carried on the ruthenium catalyst on the aluminium oxide of the present invention, the steam reforming reaction of hydrocarbon and oxygenatedchemicals will be told about below.
1. parent material (hydrocarbon, oxygenatedchemicals, and water) (1) hydrocarbon and oxygenatedchemicals
Do not do special restriction for hydro carbons that in this reaction, uses and oxygenatedchemicals.Some examples of hydro carbons roughly comprise C
1-16A linearity or a representative examples of saturated aliphatic hydro carbons be methane for example, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane; The alicyclic saturated hydrocarbons is cyclohexane for example, hexahydrotoluene, and cyclo-octene; With monocycle or polycyclic aromatic hydro carbons.Oxygenatedchemicals (idol show be called hydro carbons) hereinafter comprises for example for example methyl ether and ether of methyl alcohol and ethanol and ethers of alcohols.In addition, having boiling point is 300 ℃ or littler town gas, LPG, and naphtha is used for the methyl alcohol of petroleum industry and supplies NO with combustion system
xThe CO of reduction usefulness
2The dimethyl ether of dissolving etc. can be preferably used as parent material.The mixture of two or more of these hydro carbons also can be used as parent material.If these hydro carbons contain sulphur, then use preceding they are chosen wantonly to do the desulfurization processing, so that becoming, its sulfur content is about 1ppm or littler.Sulfur content may cause catalyst structure greater than 1ppm approximately.Method to desulfurization is not done special restriction, and some examples of this method comprise hydrogenation and suction-operated.
(2) water content
The character of the water that meeting and hydro carbons are induced reaction has no particular limits.Water can mix with hydro carbons in advance.
2. reforming reaction (1) ratio of steam/carbon
In the reforming reaction of hydro carbons, the ratio of steam/carbon is generally 1.5～10, and is preferred 1.5～5, and more preferably 2～4.When using oxygenatedchemicals, owing to can from this compound, produce oxygen, so steam can save.The method that employing is adjusted to the ratio of steam/carbon in above-mentioned scope can be produced hydrogen-rich gas.In steam reformation, use catalyst of the present invention,, still can prevent the blocking deposition even transferred to 3 or more hour at the ratio of steam/carbon.So waste heat is utilized effectively.
(2) reaction condition (2-1) reaction temperature
Reaction temperature is generally 100～900 ℃, and preferred 150～850 ℃, more preferably 200～800 ℃.Not necessarily to reserve reaction temperature in advance, because it depends on multiple factor, employed parent material in for example reacting.
2. reaction pressure
Reaction pressure is generally 0～30 kg/cm
2G, preferred 0～10kg/cm
2G.
(3) reaction method (3-1) reaction method
Both can adopt continuous flow method, also can adopt batch process, and last method be preferable.
Under the situation of continuous flow method, the gas hourly space velocity of the mist of hydro carbons and steam (GHSV) is generally 1,000～100,000h
-1, preferred 2,000～50,000h
-1, more preferably 2,000～40,000h
-1 (3-2) reaction type
Type to reaction or reactor has no particular limits.Some examples of reaction type comprise fixed bed process, pulldown bed method, and fluidized bed method.The tubular reactor still can be used as this reactor.
3. product
Contain hydrogen, methane, the mixture of carbon monoxide etc. is having under the situation of catalyst of the present invention, by the acquisition that reacts under these conditions of hydro carbons and water.Because these mixtures generally contain 50vol.% or more hydrogen, can be used to make the hydrogen of using for fuel cell suitably according to reforming method of the present invention.
The present invention will tell about by some embodiment below in detail.
Embodiment 1
Have alpha-alumina powder that particle diameter is 3～5 μ m and water (by the 20wt% of the amount of this powder) and mix to form mixture, utilize molding device at 150kgf/cm with mixer
2Under the effect, compression molding cylindrical to form (diameter 5mm, high 5mm) molded product.Molded product utilizes the waste heat of gas-fired heating furnace to carry out drying, subsequently in gas-fired furnace 1280 ℃ of following roastings 26 hours to form porous material.This material is as catalyst carrier.The crushing strength of this porous material that records with the crushing strength measurement mechanism of Kiya is at least 50kgf.Learn with X-ray diffraction analysis, by the highest peak value intensity (I that compound caused except Alpha-alumina
B) with the highest peak value intensity (I that causes by Alpha-alumina
A) ratio (I
B/ I
A) be 0.001.The micropore volume and the mean pore size that record with following method are respectively 0.26 cc/g and 1.6 μ m.
Dipping solution is by following program preparation.Ruthenium trichloride (RuCl
3NH
2O:Ru content 38%, 0.66g), magnesium nitrate (Mg (NO
3)
26H
2O, 6.36g) and cobalt nitrate (Co (NO
3) 6H
2O 2.47g), is dissolved in them in basic zirconium chloride (ZrO (OH) Cl) aqueous solution (ZC-2, Dai-ichi rare element industrial group product), is the solution of 10cc to form total measurement (volume).After stirring at least one hour, this solution is used for dipping.This maceration extract is orange red, and its pH is 0.5 or littler.This dipping utilizes the filling perforation method to be impregnated in the above-mentioned porous Alpha-alumina material of 50g.
The color of this impregnated carrier is orange, and becomes green after under 120 ℃ dry 5 hours.At last, this impregnated carrier under 500 ℃ in air roasting 2 hours to form catalyst.The ratio of these metal components of the catalyst that the component analysis demonstration is obtained is as follows: ZrO
25.0wt%, MgO 2.0wt%, Ru 0.5wt% and Co 1.0wt%.
The physical characteristic of this porous Alpha-alumina material and catalyst records in order to following method.
Micropore volume and mean pore size utilize following micropore apparatus for measuring distribution (mercury porosimeter) to adopt the mercury osmosis to measure under the following conditions.
Device: the automatic PORE SIZE APPARATUS FOR 9220 of micromeritics
Condition: catalyst is made at least 1 hour drying and is handled, subsequently according to the operation instructions of said apparatus at the pressure 50 that improves, 000psia effect is descended, and mercury is penetrated in this catalyst.Under maximum micropore volume, pore size (mid diameter) is derived from total micropore volume, and micropore distributes by mean pore size mensuration.Measurement result is summarised on the table 1.
The micropore of catalyst distributes and the BET specific area utilizes following apparatus to record under the following conditions.
Device: OMNISORP 360, made by Omnitron technology company.
Condition: with the catalyst crushing, by 16～32 order classifications.The catalyst (5g) of classification is put into specimen cup, then cup is placed on the said apparatus.Sample is evacuated to 0.1 holder or littler, then heated 3 hours down, adsorption of nitrogen to 150 holder thereupon at 300 ℃.Micropore distributes and the BET specific area is calculated according to the adsorbance of the nitrogen that obtains with adsorption method on catalyst.According to this method, micropore distribution vertical section in 2.5～2000 scopes and relevant specific area can be calculated.Result of calculation is summarised on the table 1.
This catalyst is measured with following method the reactivity agent of the steam reformation of propane.
With catalyst (1cc) the quartz reaction still pipe (internal diameter 20mm) of packing into, utilize the hydrogen steam (GHSV:6000h of hydrogen thereupon
-1) at 500 ℃ of following reductase 12s hour.Introducing propane and steam under the following conditions uses for steam reformation: reaction temperature is 450 ℃ and 550 ℃, and the GHSV of propane is 6000h
-1And the ratio (S/C)=3.0 of steam/carbon.Extract the gas that forms like this and be made for gas chromatographic analysis usefulness as sample.Analysis result calculates the reformation rate of propane by following formula.Result of calculation is shown in table 2.
Embodiment 2～14
Porous circular cylinder shape Alpha-alumina material prepares with similar method, (particle diameter: 0.5～30 μ m, 10wt%) water (amount by powder is 20wt%) is in stirrer for mixing just to have the alpha-alumina powder (90wt%) of particle diameter 3～5 μ m and bentonite.The crushing strength of this porous material is at least 50kgf.Learn with X-ray diffraction analysis, by the highest peak value intensity (I that compound caused except Alpha-alumina
B) with by highest peak value intensity (I that Alpha-alumina caused
A) ratio (I
B/ I
A) be 0.005.Micropore volume and mean pore size are respectively 0.20cc/g and 2.2 μ m.
The catalyst of embodiment 2-14 is with identical initial compounds preparation, so that carried the respective element of scheduled volume by the Alpha-alumina material.
The metallic element amount that obtains according to the component analysis to this catalyst is shown in table 1.
The physical characteristic of this porous Alpha-alumina material and catalyst and active definite with being similar to the method that is adopted among the embodiment 1.The steam reformation of propane is also passed a judgement described in embodiment 1.In embodiment 3～14, the catalytic activity under 400 ℃ and 500 ℃ of reaction temperatures is also passed a judgement.Evaluation results to these reactions is listed in the table 2.
Table 1
| The content of catalytic component (wt.%) | Specific area (m 2/g) | Ratio (the s of specific area 1/s 2) | Micropore peak value () | |||||
| Ru | Co | ZrO | MgO | Carrier (S 2) | Catalyst (S 1) | |||
| Embodiment 1 | 0.5 | 1.0 | 5.0 | 2.0 | 0.8 | 13.5 | 16.9 | 35 |
| Embodiment 2 | 0.5 | 1.0 | 5.0 | 2.0 | 0.4 | 10.4 | 26.0 | 35 |
| Embodiment 3 | 0.5 | 0 | 5.0 | 2.0 | 0.4 | 8.2 | 20.5 | 38 |
| Embodiment 4 | 0.5 | 0.06 | 5.0 | 2.0 | 0.4 | 8.5 | 21.3 | 38 |
| Embodiment 5 | 0.5 | 0.15 | 5.0 | 2.0 | 0.4 | 9.1 | 22.8 | 36 |
| Embodiment 6 | 0.5 | 0.29 | 5.0 | 2.0 | 0.4 | 9.8 | 24.5 | 34 |
| Embodiment 7 | 0.5 | 0.58 | 5.0 | 2.0 | 0.4 | 9.2 | 23.0 | 36 |
| Embodiment 8 | 0.5 | 1.00 | 5.0 | 2.0 | 0.4 | 8.6 | 21.5 | 38 |
| Embodiment 9 | 0.5 | 0.15 | 6.1 | 0.2 | 0.4 | 8.1 | 20.3 | 38 |
| Embodiment 10 | 0.5 | 0.15 | 6.1 | 3.0 | 0.4 | 8.8 | 22.0 | 36 |
| Embodiment 11 | 0.5 | 0.15 | 6.1 | 1.0 | 0.4 | 8.2 | 20.5 | 38 |
| Embodiment 12 | 0.5 | 0.15 | 6.1 | 0.5 | 0.4 | 8.2 | 20.5 | 38 |
| Embodiment 13 | 0.5 | 0.15 | 6.1 | 2.0 | 0.4 | 8.6 | 21.5 | 36 |
| Embodiment 14 | 0.5 | 0.15 | 6.1 | 0.0 | 0.4 | 8.1 | 20.3 | 38 |
Annotate: Ru; Ruthenium Co; Cobalt ZrO; Zirconium dioxide MgO; Magnesia
Table 2
| The conversion ratio of propane (%) | ||||
| 400℃ | 450℃ | 500℃ | 550℃ | |
| Embodiment 1 | --- | 25 | --- | 94 |
| Embodiment 2 | --- | 21 | --- | 92 |
| Embodiment 3 | 2.0 | 12 | 58 | 84 |
| Embodiment 4 | 2.4 | 11 | 41 | 85 |
| Embodiment 5 | 4.4 | 22 | 88 | 93 |
| Embodiment 6 | 5.7 | 28 | 94 | 94 |
| Embodiment 7 | 4.6 | 23 | 93 | 91 |
| Embodiment 8 | 2.7 | 12 | 43 | 82 |
| Embodiment 9 | 0.8 | 1 | 8 | 7 |
| Embodiment 10 | 4.5 | 23 | 92 | 91 |
| Embodiment 11 | 0.9 | 4 | 14 | 52 |
| Embodiment 12 | 0.3 | 1 | 3 | 10 |
| Embodiment 13 | 3.2 | 14 | 50 | 68 |
| Embodiment 14 | 1.4 | 4 | 10 | 19 |
As what from table 1 and table 2, see significantly, have bigger serface and pore size less than 1000 the two the catalyst of embodiment 1 and the catalyst of embodiment 2 demonstrate high propane reformation rate and catalytic activity.
As mentioned above, the ruthenium catalyst that is carried on the aluminium oxide of the present invention contains the porous Alpha-alumina material as the regulation of catalyst carrier, and this catalyst demonstrates good crushing strength.Therefore, catalyst of the present invention can not break in the reforming reaction still, and can prevent catalyst layer and pipeline obstruction.Catalyst of the present invention has the specific area 7～50m that has increased
2/ g, this facilitates bearing metal component effectively.In catalyst of the present invention, ruthenium component of being carried and the cobalt component of choosing wantonly and magnesium component all near the zirconium component, are the high degree of dispersion state and have good stability.When being used for the steam reformation of hydrocarbon, it demonstrates per unit and contains the ruthenium component high catalytic activity and good hear resistance are arranged.This high catalytic activity can at high temperature keep satisfactorily.With regard to cost and catalytic activity two aspects, catalyst of the present invention is particularly suitable for making the steam reformation of the hydrogen of using for fuel cell.So this catalyst has very big value industrial.
Claims (7)
1. a ruthenium catalyst that is carried on the aluminium oxide comprises a kind of ruthenium component by the carrying of porous Alpha-alumina material, the specific area (S that this catalyst has
1) be 7～50m
2/ g, the described specific area (S that is carried on the ruthenium catalyst on the aluminium oxide
1) with the specific area (S of porous Alpha-alumina material
2) ratio be 3-50, described catalyst is used for the steam reforming reaction of hydrocarbon and oxygenatedchemicals.
2. according to the ruthenium catalyst on the aluminium oxide of being carried on of claim 1, the specific area (S that catalyst wherein has
1) be 8～20m
2/ g.
3. the ruthenium catalyst that is carried on the aluminium oxide comprises at least a ruthenium component by the carrying of porous Alpha-alumina material, and at least one peak value dropped in 5～1000 scopes during the micropore that this catalyst has distributed, and the specific area (S that has
1) be 7～50m
2/ g, described catalyst is used for the steam reforming reaction of hydrocarbon and oxygenatedchemicals.
4. according to the ruthenium catalyst on the aluminium oxide of being carried on of claim 1, porous Alpha-alumina material wherein and ruthenium component and zirconium component dipping, their content separately is: it is 0.05～5 weight % that the ruthenium components contents is converted elements ruthenium, and the zirconium components contents to convert zirconia be 0.05～20 weight %, wherein all percentage all are to calculate with respect to the weight of porous Alpha-alumina material.
5. according to the ruthenium catalyst on the aluminium oxide of being carried on of claim 1, porous Alpha-alumina material wherein adopts the ruthenium component, the zirconium component, with alkaline-earth metal or rare earth metal component dipping, their content separately is: it is 0.05～5 weight % that the ruthenium components contents is converted elements ruthenium, it is 0.05～20 weight % that the zirconium components contents is converted zirconia, and alkaline-earth metal or rare earth metal components contents to convert its corresponding oxide be 0.5～20 weight %, wherein all percentage all are to calculate with respect to the weight of porous Alpha-alumina.
6. according to the ruthenium catalyst on the aluminium oxide of being carried on of claim 1, porous Alpha-alumina wherein adopts the ruthenium component, the zirconium component, alkaline-earth metal or rare earth metal component, and cobalt component dipping, their content separately is: it is 0.05～5 weight % that the ruthenium components contents is converted elements ruthenium, it is 0.05～20 weight % that the zirconium components contents is converted zirconia, it is 0.5～20 weight % that alkaline-earth metal or rare earth metal components contents are converted its corresponding oxide, wherein all percentage all are to calculate with respect to the weight of porous Alpha-alumina, and the cobalt component is to be that 0.01～30 condition is introduced by cobalt (Co) and (Ru) mol ratio Co/Ru.
7. according to the ruthenium catalyst on the aluminium oxide of being carried on of claim 1, alkaline earth metal component wherein is a magnesium.
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| FR2932701B1 (en) * | 2008-06-20 | 2011-06-17 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION CATALYST AND PROCESS FOR PREPARING THE SAME |
| WO2010134077A2 (en) * | 2009-05-20 | 2010-11-25 | Yeda Research And Development Co. Ltd. | Catalytic gasification of organic matter in supercritical water |
| EP2409759A1 (en) * | 2010-07-23 | 2012-01-25 | LANXESS Deutschland GmbH | Isomerisation catalyst |
| CN104801333B (en) * | 2015-03-03 | 2017-12-19 | 新奥科技发展有限公司 | A kind of preparation method of loading type nickel-based catalyst |
| CN110947379B (en) * | 2019-12-23 | 2020-08-18 | 中国矿业大学 | Preparation of high-activity ruthenium catalyst and application of high-activity ruthenium catalyst in room-temperature catalytic hydrogenation |
| CN113025839B (en) * | 2021-03-03 | 2021-11-26 | 西北有色金属研究院 | Preparation method of microalloyed molybdenum-ruthenium alloy |
| CN113393955B (en) * | 2021-08-13 | 2021-11-16 | 西安宏星电子浆料科技股份有限公司 | LTCC co-fired matching type resistance paste |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495861A (en) * | 1972-03-20 | 1974-01-19 | ||
| US4579985A (en) * | 1983-11-15 | 1986-04-01 | Shell Oil Company | Process for the preparation of hydrocarbons |
| CN1108637A (en) * | 1993-12-24 | 1995-09-20 | 三菱化学株式会社 | Method for producing a cycloolefin |
| JPH0929097A (en) * | 1995-07-21 | 1997-02-04 | Idemitsu Kosan Co Ltd | Steam reforming catalyst of hydrocarbon |
-
1997
- 1997-11-27 CN CN97182511A patent/CN1104950C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495861A (en) * | 1972-03-20 | 1974-01-19 | ||
| US4579985A (en) * | 1983-11-15 | 1986-04-01 | Shell Oil Company | Process for the preparation of hydrocarbons |
| CN1108637A (en) * | 1993-12-24 | 1995-09-20 | 三菱化学株式会社 | Method for producing a cycloolefin |
| JPH0929097A (en) * | 1995-07-21 | 1997-02-04 | Idemitsu Kosan Co Ltd | Steam reforming catalyst of hydrocarbon |
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