CN101636471B - Process for production of hydrocarbons by reduction of carbon monoxide - Google Patents
Process for production of hydrocarbons by reduction of carbon monoxide Download PDFInfo
- Publication number
- CN101636471B CN101636471B CN200880005002.2A CN200880005002A CN101636471B CN 101636471 B CN101636471 B CN 101636471B CN 200880005002 A CN200880005002 A CN 200880005002A CN 101636471 B CN101636471 B CN 101636471B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zirconium
- reduction
- carbon monoxide
- carrier
- 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000000694 effects Effects 0.000 description 14
- 238000004453 electron probe microanalysis Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 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 2
- 239000002245 particle Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- SDXDHLDNCJPIJZ-UHFFFAOYSA-N [Zr].[Zr] Chemical compound [Zr].[Zr] SDXDHLDNCJPIJZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KAHROJAJXYSFOD-UHFFFAOYSA-J triazanium;zirconium(4+);tricarbonate;hydroxide Chemical compound [NH4+].[NH4+].[NH4+].[OH-].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KAHROJAJXYSFOD-UHFFFAOYSA-J 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
Abstract
In a process for producing hydrocarbons by reduction of carbon monoxide, operation without run away reaction can be continued by subjecting a catalyst which comprises both cobalt as active metal and a carrier supporting the cobalt which carrier comprises a metal oxide and zirconium supported on the metal oxide and in which at least 60% of the whole zirconium is present in the 49vol% outer surfaceside zone of the carrier to reduction in a hydrogen atmosphere at 410 to 470 DEG C for 4 to 12 hours and then using the resulting catalyst in the reduction of carbon monoxide.
Description
Invention field
The present invention relates to the also method of original production hydrocarbon by carbon monoxide.
Background of invention
In recent years, than having strengthened quickly in the past about the liquid fuel regulation of the sulfur content of gasoline and diesel oil for example.Therefore, definitely be necessary to produce at present sulphur and the less eco-friendly clean fuel liquid of arene content.With the hydrogen reducing carbon monoxide be Fischer-Tropsch (FT) synthetic be an example producing the method for such clean fuel.
Fischer-Tropsch is synthetic use comprise the reactive metal that loads on carrier such as silica or the aluminium oxide for example the catalyst of ruthenium or cobalt carry out (for example, face patent documentation 1) as follows.General with these reactive metals of hydrogen reducing before the synthetic beginning of FT.
It is reported that these catalyst improve catalytic performance (for example, face patent documentation 2) as follows by using second metal with the combination of such reactive metal.The example of second metal comprises sodium, magnesium, lithium, zirconium and hafnium, and it depends on that purpose for example improves the carbon monoxide conversion ratio and increase chain growth probability (α) is used suitably, and described chain growth probability will be the index of wax growing amount.
(1) patent documentation 1: the Japan Patent spy opens and announces No.4-227847
(2) patent documentation 2: the Japan Patent spy opens and announces No.59-102440
FT is synthetic to be the reaction of kind of very big heat release, therefore usually when carrying out by this reaction system of external refrigeration or allow solvent coexist as wherein to shift out heat.To carry out ground bad if heat shifts out, and the temperature in the catalyst layer sharply rises and runaway reaction, if the worst situation takes place then the generation that causes burning.One of factor that heat is shifted out become difficulty is the high activity of catalyst.Generally speaking, if catalyst is highly active, it can reduce reaction temperature, makes it possible to improve the yield of the hydrocarbon with higher molecular weight and prolongs life of catalyst.Yet on the other hand, because the high activity of catalyst, heat might produce the part in catalyst layer, and therefore runaway reaction takes place.As mentioned above, the raising of catalyst activity cause at process aspect unfavorable.
Summary of the invention
The reduction of carbon monoxide is the reaction of very big heat release, therefore tends to out of control.This tendency becomes obvious when catalyst activity is higher.Therefore, in view of processing safety, wish to reduce activity of such catalysts.Simultaneously, in order to improve the economic benefit of this method, think that the raising of catalyst activity is indispensable.These contradiction aspects of catalyst activity have hindered the exploitation of the high FT synthetic method of economic benefit.
As the inventor's broad research and the result of exploitation, the following discovery that the present invention is based on them is accomplished: specific catalyst was reduced before being used for the carbon monoxide reduction under given conditions handle and to use such catalyst to carry out FT synthetic, cause the operation of its high activity and safety.
Namely, the present invention relates to produce the method for hydrocarbon, this method may further comprise the steps: under hydrogen atmosphere under 410 ℃-470 ℃ temperature with catalyst reduction 4-12 hour, with the reduction that this catalyst is used for carbon monoxide, this catalyst comprises as reactive metal and loads on cobalt on the carrier, described carrier comprises metal oxide and loads on zirconium on the described metal oxide, 60% or be present in from the zone of the outer surface 49 volume % of described carrier of zirconium gross mass more.
In the method for above-mentioned production hydrocarbon, metal oxide is preferably aluminium oxide or silica.
In the method for above-mentioned production hydrocarbon, the load capacity of zirconium is preferably the 1.0-8.0 quality % of metal oxide.
In the method for above-mentioned production hydrocarbon, the load capacity of cobalt is preferably the 20-40 quality % of carrier.
The invention effect
The present invention makes and might carry out the carbon monoxide restoring operation safely and not cause reaction out of control from the starting stage, although this catalyst is highly active FT synthetic catalyst by prereduction specific catalyst under given conditions.
Implement optimal mode of the present invention
Below the present invention will be described in further detail.
In the present invention, use to comprise carrier and to load on the catalyst of the cobalt on this carrier as reactive metal, described carrier makes by zirconium is loaded on the metal oxide.
There is not particular restriction to being used for metal oxide of the present invention.The example of metal oxide comprises silica, titanium dioxide, aluminium oxide and magnesia.Preferred example comprises silica and aluminium oxide.
Character to metal oxide does not have particular restriction.Yet the specific area of the metal oxide that records by nitrogen adsorption method is preferably 100-800m
2/ g, more preferably 150-500m
2/ g.
The average pore size of described metal oxide is preferably 6-30nm, more preferably 10-15nm.If the average pore size of metal oxide less than 6nm or greater than 30nm, then is not preferred, because can not produce highly active catalyst.
Shape to metal oxide does not have particular restriction.In view of practicality, this shape is preferably the sphere of using in actual oil plant or the petrochemical industry unit, cylindrical or trilobal.Particle diameter there is not particular restriction yet.Yet in view of practicality, particle diameter is preferably 10 μ m-10mm.
In the present invention importantly, 60% of the zirconium gross mass or more multi-load from the zone (hereinafter also being called " outer surface near zone ") of carrier outer surface 49 volume %.The amount that is present in the zirconium in the outer surface near zone be preferably total zirconium amount 70% or more, more preferably 80% or more.
If be present in the amount of the zirconium in the described outer surface near zone less than 60% of total zirconium amount, the gained catalyst might catalytic activity reduce and therefore weaken effect of the present invention.In the present invention, term " from the zone of carrier outer surface 49 volume % " refers to that from the zone of carrier outer surface towards its center this regional volume is 49 volume % of carrier cumulative volume.
For ball type carrier, the volume of 1/5 radius region from the outer surface to the center (outer surface side) is corresponding to 49% of ball type carrier cumulative volume.Therefore, in this case, refer to from the zone of carrier outer surface 49 volume % from the outer surface of carrier 1/5 radius region towards its center.
By measure the zirconium concentration at each some place with electron probe microanalysis (EPMA) (EPMA), obtain along the zirconium CONCENTRATION DISTRIBUTION of the radial direction of carrier granular.
The load capacity of zirconium is generally the 0.2-15 quality % of metal oxide, preferred 1.0-8.0 quality %.If should measure less than 0.2 quality %, the catalytic activity of gained catalyst will reduce.If should measure greater than 15 quality %, will stop up the hole of metal oxide, cause the tendency of the catalytic activity reduction of catalyst.
There is not particular restriction for the method in the outer surface near zone that zirconium is loaded on metal oxide.Can use several different methods, for example infusion process, incipient wetness method and LPD (liquid deposition) method, preferably LPD method.
The method for optimizing that production has the catalyst of carrier (zirconium of its middle and high concentration loads in the outer surface near zone of above-mentioned metal oxide) can be following method.
At first, above-mentioned metal oxide pH be 7 or the lower aqueous solution carry out preliminary treatment.PH be 7 or the example of the lower aqueous solution comprise aqueous solution of nitric acid, acetic acid aqueous solution, aqueous sulfuric acid, aqueous hydrochloric acid solution, ion exchange water and distilled water.Described pH is preferably 5-7, more preferably 6-7.Being lower than 5 pH is not preferred on economic implications, and this is because it has improved the necessity that increases the concentration of the zirconium of wanting load after the preliminary treatment.For example, can by with pH be 7 or the lower aqueous solution inject the container that fills metal oxide and carry out preliminary treatment.
Metal oxide pH be 7 or the lower aqueous solution in soak time be 10-72 hour for leaving standstill situation, be 1-12 hour and be 1-30 minute for being exposed to hyperacoustic situation for the jolting situation.In any situation, even metal oxide is soaked the time longer than required time in solution, it does not affect adversely yet.The above-mentioned time is applicable to that solution temperature is the situation of room temperature.Can shorten soak time by solution being heated to 50 ℃.When solution temperature was higher than 50 ℃, it was not preferred, and this is because water with potential evaporation, causes pH to change.
After carrying out the preliminary treatment scheduled time, can be injected in the container that fills this pretreated metal oxide by the solution with excessive zirconium zirconium is loaded on this metal oxide.Then, preferably remove the supernatant of pretreated solution, because can use less container.Term used herein " excessive " refers to the twice of metal oxide volume or more times volume.
Zirconium used herein source can be zirconium oxysulfate, zirconyl acetate, zirconium carbonate ammonium (Ammoniumzirconyl carbonate) or tri-chlorination zirconium, and preferably zirconium carbonate ammonium or zirconyl acetate.
The time used to the load zirconium does not have particular restriction, because this time is depended on the zirconium amount of wanting for the treatment of load.Yet, it typically is 3-72 hour.
After the load zirconium is finished, carrier (metal oxide of load zirconium) and solution separated and dry then.Drying means there is not particular restriction.The example of drying means is included in air dry and degassing drying in a vacuum in the air.Under 100-200 ℃, preferred 110-130 ℃ temperature, carried out dry 2-24 hour, preferred 5-12 hour.
After dry the processing, calcine that zirconium is converted into oxide.Method for calcinating there is not particular restriction.Calcining was carried out 1-5 hour under 340-600 ℃, preferred 400-450 ℃ temperature under air atmosphere usually.
Like this, produced carrier, this carrier comprises metal oxide and optionally loads on the oxide of the zirconium in the outer surface near zone of this metal oxide.
Then, cobalt is loaded on this carrier, in this carrier, zirconium loads on the metal oxide.Usually, being used for the synthetic reactive metal of FT can be ruthenium, cobalt or iron.Yet, use cobalt in the present invention as reactive metal in order to utilize the characteristic of zirconium.
The amount of the cobalt of load can be the preferred 10-50 quality % of carrier, more preferably 20-40 quality %.If should amount less than 10 quality %, the gained activity of such catalysts is deficiency, and therefore can not obtain effect of the present invention.If should amount surpass 50 quality %, coalescent and therefore cobalt will may will reduce the gained catalyst as the practical value of actual FT synthetic catalyst.
Method to the load cobalt does not have particular restriction.Can use for example incipient wetness method of infusion process.
The precursor compound that is used for the load cobalt there is not particular restriction.Therefore, can use salt or the complex compound of cobalt.Example comprises nitrate, hydrochloride, formates, propionate and acetate.
After the cobalt load, usually under temperature 100-200 ℃, preferred 110-130 ℃ temperature dry 2-24 hour, preferred 5-10 hour, then under air atmosphere in 340-600 ℃, preferred 400-450 ℃ temperature lower calcination 1-5 hour so that cobalt is converted into oxide, thereby make the catalyst that is used for the reduction carbon monoxide that uses among the present invention.
When using the catalyst reduction carbon monoxide of above preparation, this catalyst is carried out the prereduction processing so that it shows its activity.It is very important that this prereduction is handled for the present invention, and if it carry out in unsuitable mode, when using this catalyst to be used for the carbon monoxide reduction, reaction temperature will uncontrollably rise.
In the present invention, the reduction of carrying out catalyst under hydrogen atmosphere is handled.Reduction temperature is 410-470 ℃, preferred 420-450 ℃.The reduction temperature that is lower than 410 ℃ is not preferred, because activity often reduces when this catalyst is used for the carbon monoxide reduction.The reduction temperature that is higher than 470 ℃ is not preferred, because it causes very big temperature rise when this catalyst is used for the carbon monoxide reduction, the possibility that has caused runaway reaction to occur is very big and therefore can not obtain expected effect of the present invention.
Recovery time is preferably 4-12 hour, more preferably 5-12 hour.The recovery time that is shorter than 4 hours is not preferred, because its often active reduction when this catalyst is used for the carbon monoxide reduction.The recovery time of being longer than 12 hours is not preferred, and this is because it causes very big temperature rise when this catalyst is used for the carbon monoxide reduction, has caused the possibility of runaway reaction very big and so can not obtain expected effect of the present invention.
As mentioned above, the reduction of using the catalyst that carried out the prereduction processing under given conditions to be used for carbon monoxide can produce hydrocarbon and not cause runaway reaction, even this catalyst is highly active.
Embodiment
Hereinafter, will more at large describe the present invention by following examples and Comparative Examples, it should not be construed as and limits the scope of the invention.
The preparation of catalyst 1
With the preparing spherical SiO 2 of 30g (average pore size: 10nm, average grain diameter: 1.8mm) be weighed in the 250mL vial and to wherein adding the 100ml ion exchange water.Under 40 ℃ temperature, applied ultrasonic wave 30 minutes to this mixture.Extract the supernatant of about 50mL then with P Pasteur pipette out, add the 0.1mol/L zirconium carbonate ammonium aqueous solution of 150mL then.Allow this mixture at room temperature leave standstill 24 hours.Thereafter, with filter paper filter this mixture and then in a vacuum under 120 ℃ the temperature dry 6 hours and under air atmosphere in 430 ℃ temperature lower calcination 3 hours.
By incipient wetness method with cobalt nitrate aqueous solution dipping gained contain the zirconium carrier, the amount of cobalt nitrate accounts for 30 quality % of carrier in metallic cobalt.With carrier under 120 ℃ temperature dry 12 hour and 420 ℃ temperature lower calcination 3 hour, thereby produce the catalyst 1 wanted thereafter.
Use fluorescent X-ray that the amount of zirconium in this catalyst is carried out quantitatively.In addition, measure zirconium along CONCENTRATION DISTRIBUTION and the amount of catalyst radial direction by electron probe microanalysis (EPMA) (EPMA).Table 1 has provided the ratio of amount with the total amount of zirconium of the zirconium that exists in the zone (outer surface side) of the amount of zirconium in this catalyst and 1/5 radius from the outer surface to the center.
The preparation of catalyst 2
Be weighed into 30g embodiment 1 used preparing spherical SiO 2 in the 250ml vial and to wherein adding the 100ml ion exchange water.Under 40 ℃ temperature, applied ultrasonic wave 10 minutes to this mixture.Extract about 50ml supernatant out with the Pasteur pipette then, add the zirconium carbonate ammonium aqueous solution of the 0.3mol/L of 150ml then.Allow this mixture at room temperature leave standstill 30 hours.Thereafter, with filter paper filter this mixture and then in a vacuum under 120 ℃ temperature dry 6 hours and in air atmosphere in 430 ℃ temperature lower calcination 3 hours.
By incipient wetness method with cobalt nitrate aqueous solution dipping gained contain the zirconium carrier, the amount of cobalt nitrate accounts for 25 quality % of carrier in metallic cobalt.With carrier under 120 ℃ temperature dry 12 hour, then 420 ℃ temperature lower calcination 3 hour, thereby produce the catalyst 2 wanted thereafter.
Use fluorescent X-ray that the amount of zirconium in this catalyst is carried out quantitatively.In addition, measure zirconium along CONCENTRATION DISTRIBUTION and the amount of catalyst radial direction by electron probe microanalysis (EPMA) (EPMA).Table 1 has provided the ratio of amount with the total amount of zirconium of the zirconium that exists in the zone (outer surface side) of the amount of zirconium in this catalyst and 1/5 radius from the outer surface to the center.
The preparation of catalyst 3
Prepare catalyst 3 by the same program that is used for catalyst 1, difference is to contain the aqueous solution of nitric acid dipping of 1.2g zirconium for the preparation of the 30g silica of catalyst 1 by incipient wetness method usefulness.The result provides in table 1.
Use fluorescent X-ray that the amount of zirconium in this catalyst is carried out quantitatively.In addition, measure zirconium along CONCENTRATION DISTRIBUTION and the amount of catalyst radial direction by electron probe microanalysis (EPMA) (EPMA).Table 1 has provided the ratio of amount with the total amount of zirconium of the zirconium that exists in the zone (outer surface side) of the amount of zirconium in the catalyst and 1/5 radius from the outer surface to the center.
Table 1
| The amount of zirconium (quality %) in the catalyst | The ratio (%) of the amount of the zirconium that exists in the 1/5 catalyst outer surface side | |
| Catalyst 1 | 2.0 | 65 |
| Catalyst 2 | 3.2 | 87 |
| Catalyst 3 | 3.6 | 38 |
Embodiment 1
10g catalyst 1 is joined in the fixed bed circular form reactor.Under the temperature of the pressure of 3MPa and 410 ℃ with catalyst 1 at hydrogen stream (flow: 30 ml/min) reduction 5 hours down.Use synthesis gas (hydrogen/carbon monoxide mol ratio=2.1) as raw material and use this catalyst at 220 ℃ initial temperature, pressure and the 1800h of 3MPa thereafter,
-1Gas hourly space velocity under reduce.The carbon monoxide conversion ratio that monitors between the stage of reaction and the rising of the peak temperature in the catalyst layer in following table 2, have been provided.
Embodiment 2
Carry out the reduction of carbon monoxide according to the program of embodiment 1, difference is that the temperature of reducing catalyst is 450 ℃.In table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Embodiment 3
Carry out the reduction of carbon monoxide according to the program of embodiment 1, difference is that the temperature of reducing catalyst is 470 ℃.In table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Embodiment 4
Carry out the reduction of carbon monoxide according to the program of embodiment 2, difference is to use catalyst 2 to replace catalyst 1.In table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Comparative Examples 1
Carry out the reduction of carbon monoxide according to the program of embodiment 1, difference is that the temperature of reducing catalyst is 400 ℃.In following table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Comparative Examples 2
Carry out the reduction of carbon monoxide according to the program of embodiment 1, difference is that the temperature of reducing catalyst is 480 ℃.In following table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Comparative Examples 3
Carry out the reduction of carbon monoxide according to the program of embodiment 2, difference is to use catalyst 3 to replace catalyst 1.In table 2, provided the rising of peak temperature in the carbon monoxide conversion ratio that monitors between the stage of reaction and the catalyst layer.
Table 2
| Carbon monoxide conversion ratio (mole %) | The rising of peak temperature in the catalyst layer (℃) | |
| Embodiment 1 | 70.1 | 4 |
| Embodiment 2 | 72.6 | 7 |
| Embodiment 3 | 73.2 | 10 |
| Embodiment 4 | 81.0 | 12 |
| Comparative Examples 1 | 51.8 | 1 |
| Comparative Examples 2 | 100 | ＞200 (out of control) |
| Comparative Examples 3 | 58.6 | 2 |
As mentioned above, confirmed in the carbon monoxide reduction of the catalyst of working load cobalt, wherein the zirconium amount that exists the zone of 1/5 radius from the carrier outer surface to its center (outer surface side) is 60% or more, by under hydrogen atmosphere under 410-470 ℃ temperature with catalyst reduction 4-12 hour, it is out of control that but inhibitory reaction did not take place from the starting stage of reaction, even this catalyst is highly active FT synthetic catalyst.
Industrial applicibility
Therefore method of the present invention is for also the original production hydrocarbon is exceedingly useful and have a very big industrial value by carbon monoxide.
Claims (4)
1. produce the method for hydrocarbon, may further comprise the steps:
Under hydrogen atmosphere under 420-470 ℃ temperature with catalyst reduction 4-12 hour; With
With the reduction of described catalyst for carbon monoxide,
Described catalyst comprises as reactive metal and loads on cobalt on the carrier, and described carrier comprises metal oxide and loads on zirconium on the described carrier, 60% or be present in from the zone of the outer surface side 49 volume % of described carrier of zirconium gross mass more.
2. according to the method for the production hydrocarbon of claim 1, wherein said metal oxide is aluminium oxide or silica.
3. according to the method for the production hydrocarbon of claim 1 or 2, wherein the load capacity of zirconium is the 1.0-8.0 quality % of described metal oxide.
4. according to the method for each production hydrocarbon in the claim 1 to 3, wherein the load capacity of cobalt is the 20-40 quality % of described carrier.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP033037/2007 | 2007-02-14 | ||
| JP2007033037 | 2007-02-14 | ||
| PCT/JP2008/051712 WO2008099695A1 (en) | 2007-02-14 | 2008-01-29 | Process for production of hydrocarbons by reduction of carbon monoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101636471A CN101636471A (en) | 2010-01-27 |
| CN101636471B true CN101636471B (en) | 2013-09-25 |
Family
ID=39689939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880005002.2A Expired - Fee Related CN101636471B (en) | 2007-02-14 | 2008-01-29 | Process for production of hydrocarbons by reduction of carbon monoxide |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP5127726B2 (en) |
| CN (1) | CN101636471B (en) |
| AU (1) | AU2008215570B2 (en) |
| MY (1) | MY148931A (en) |
| RU (1) | RU2449002C2 (en) |
| WO (1) | WO2008099695A1 (en) |
| ZA (1) | ZA200905535B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5025301B2 (en) * | 2007-03-28 | 2012-09-12 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrocarbon production method |
| JP5676120B2 (en) * | 2010-02-26 | 2015-02-25 | Ｊｘ日鉱日石エネルギー株式会社 | Process for producing activated Fischer-Tropsch synthesis catalyst and process for producing hydrocarbon |
| JP5795483B2 (en) * | 2011-03-31 | 2015-10-14 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Activated Fischer-Tropsch synthesis reaction catalyst and hydrocarbon production method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386821A (en) * | 2001-05-18 | 2002-12-25 | 石油大学(北京) | Fischer-Tropsch catalyst and its preparing process |
| CN1398669A (en) * | 2002-07-19 | 2003-02-26 | 中国科学院山西煤炭化学研究所 | Co-Zr catalyst for Fischer-Tropsch synthesis and its prepn and application |
| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
| EP1736239A1 (en) * | 2004-04-16 | 2006-12-27 | Nippon Oil Corporation | Catalyst for fisher-tropsh synthesis and method for producing hydrocarbon |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3365337D1 (en) * | 1982-11-22 | 1986-09-18 | Shell Int Research | Process for the preparation of a fischer-tropsch catalyst, a catalyst so prepared and use of this catalyst in the preparation of hydrocarbons |
| CA1312066C (en) * | 1986-10-03 | 1992-12-29 | William C. Behrmann | Surface supported particulate metal compound catalysts, their use in hydrocarbon synthesis reactions and their preparation |
| US5652193A (en) * | 1989-03-29 | 1997-07-29 | Exxon Research And Engineering Company | Method for hydrocarbon synthesis reactions |
| GB8925979D0 (en) * | 1989-11-16 | 1990-01-04 | Shell Int Research | Process for the preparation of extrudates,extrudates,and use of the extrudates |
| CA2093441C (en) * | 1990-10-15 | 2001-12-11 | William Claus Behrmann | Method for preparing cobalt-containing hydrocarbon synthesis catalyst |
| DZ2013A1 (en) * | 1995-04-07 | 2002-10-23 | Sastech Ltd | Catalysts. |
| AU764183B2 (en) * | 1999-05-26 | 2003-08-14 | Sasol Technology (Uk) Limited | Improved fischer-tropsch activity for "non-promoted" cobalt-on-alumina catalysts |
| AR028067A1 (en) * | 2000-05-04 | 2003-04-23 | Shell Int Research | A CATALYST SUPPORT AND A SUPPORTED METAL CATALYST, A PROCESS FOR ITS PREPARATION AND THE USE OF THE CATALYST |
| WO2006099897A1 (en) * | 2005-03-22 | 2006-09-28 | Eastman Kodak Company | Method and device for controlling differential gloss and print item produced thereby |
| US20070055963A1 (en) * | 2005-09-08 | 2007-03-08 | Lucent Technologies, Inc. | Compile target and compiler flag extraction in program analysis and transformation systems |
-
2008
- 2008-01-29 CN CN200880005002.2A patent/CN101636471B/en not_active Expired - Fee Related
- 2008-01-29 RU RU2009134169/04A patent/RU2449002C2/en not_active IP Right Cessation
- 2008-01-29 MY MYPI20093348A patent/MY148931A/en unknown
- 2008-01-29 AU AU2008215570A patent/AU2008215570B2/en not_active Ceased
- 2008-01-29 ZA ZA200905535A patent/ZA200905535B/en unknown
- 2008-01-29 WO PCT/JP2008/051712 patent/WO2008099695A1/en active Application Filing
- 2008-01-29 JP JP2008558040A patent/JP5127726B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386821A (en) * | 2001-05-18 | 2002-12-25 | 石油大学(北京) | Fischer-Tropsch catalyst and its preparing process |
| CN1398669A (en) * | 2002-07-19 | 2003-02-26 | 中国科学院山西煤炭化学研究所 | Co-Zr catalyst for Fischer-Tropsch synthesis and its prepn and application |
| EP1736239A1 (en) * | 2004-04-16 | 2006-12-27 | Nippon Oil Corporation | Catalyst for fisher-tropsh synthesis and method for producing hydrocarbon |
| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008099695A1 (en) | 2010-05-27 |
| CN101636471A (en) | 2010-01-27 |
| AU2008215570B2 (en) | 2012-05-10 |
| MY148931A (en) | 2013-06-14 |
| WO2008099695A1 (en) | 2008-08-21 |
| RU2009134169A (en) | 2011-03-20 |
| JP5127726B2 (en) | 2013-01-23 |
| ZA200905535B (en) | 2010-10-27 |
| AU2008215570A1 (en) | 2008-08-21 |
| RU2449002C2 (en) | 2012-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102770204B (en) | Process for production of activated fischer-tropsch synthesis catalyst, and process for production of hydrocarbon | |
| KR101026536B1 (en) | Fe-based catalyst for the reaction of Fischer-Tropsch synthesis and preparation method thereof | |
| CA2048330C (en) | Hydrotreating catalyst: composition, preparation, and use thereof | |
| CN102781574B (en) | Fischer-tropsch synthesis catalyst, manufacturing method therefor, and hydrocarbon manufacturing method | |
| CN104841465A (en) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof | |
| CN112808273B (en) | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed | |
| US4233180A (en) | Process for the conversion of carbon monoxide | |
| CN101636471B (en) | Process for production of hydrocarbons by reduction of carbon monoxide | |
| CN108079988A (en) | The catalyst of C5, C6 alkane isomerization and preparation and application | |
| CN108671947B (en) | Ni for hydrodeoxygenation of bio-oil2P/reduced graphene oxide catalyst and preparation method thereof | |
| RU2548000C2 (en) | Production of hydrocarbons | |
| CN110038591B (en) | Copper-iridium composite oxide catalyst for preparing methanol by methane oxidation | |
| CN1916121B (en) | Method for preparing diene selective hydrotreating catalyst for gasoline | |
| US2878193A (en) | Preparation of iron group hydrogenation catalyst support on molybdenum oxide-aluminasupport | |
| CN111822003B (en) | Iron-based catalyst and preparation method and application thereof | |
| CN112206812B (en) | Preparation and application of metal modified isolated iron site catalyst | |
| JPS63123448A (en) | Manufacture of hydrogenating treating catalyst from hydrogel | |
| CN112892569A (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by selective oxidation of hydrogen sulfide under medium-high temperature condition by using same | |
| CA3188249A1 (en) | Molybdenum carbide catalysts | |
| KR101248116B1 (en) | Process for preparing nano-metal phosphide supported catalyst | |
| CN112604709A (en) | Hydrogenation catalyst for treating sulfur-containing waste gas and application thereof | |
| CN113967474A (en) | Low-carbon alkane dehydrogenation catalyst and preparation method thereof | |
| FI59118C (en) | FOERFARANDE FOER KATALYTISK HYDROAVSVAVLING AV RESTKOLVAETEOLJOR | |
| CN112387276A (en) | Supported ruthenium cluster catalyst for ammonia synthesis and preparation method and application thereof | |
| US4040979A (en) | Hydrocarbon conversion catalytic composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130925 Termination date: 20190129 |