WO2001026805A1 - Catalyseur d'hydroraffinage de distillat, son milieu et sa preparation - Google Patents

Catalyseur d'hydroraffinage de distillat, son milieu et sa preparation Download PDF

Info

Publication number
WO2001026805A1
WO2001026805A1 PCT/CN2000/000318 CN0000318W WO0126805A1 WO 2001026805 A1 WO2001026805 A1 WO 2001026805A1 CN 0000318 W CN0000318 W CN 0000318W WO 0126805 A1 WO0126805 A1 WO 0126805A1
Authority
WO
WIPO (PCT)
Prior art keywords
alumina
catalyst
reaction
sodium
catalyst according
Prior art date
Application number
PCT/CN2000/000318
Other languages
English (en)
French (fr)
Inventor
Qinghe Yang
Bin Liu
Hong Nie
Xuefen Liu
Dadong Li
Yahua Shi
Fucheng Zhuang
Original Assignee
China Petrochemical Corporation
Research Institute Of Petroleum Processing, Sinopec
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petrochemical Corporation, Research Institute Of Petroleum Processing, Sinopec filed Critical China Petrochemical Corporation
Priority to CN00802168A priority Critical patent/CN1124890C/zh
Priority to AU78986/00A priority patent/AU7898600A/en
Priority to EP00969164A priority patent/EP1142637B1/en
Publication of WO2001026805A1 publication Critical patent/WO2001026805A1/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis

Definitions

  • the invention relates to a distillate hydrorefining catalyst, a preparation method thereof, a support for the catalyst, and a preparation method thereof. More specifically, it relates to a tritium oil refining catalyst containing a Group VIB metal and / or metal oxide and a Group VIII metal and / or metal oxide, a preparation method thereof, and an alumina support thereof, and Method for preparing the alumina carrier.
  • hydrotreating catalyst is the most important and key technology in this process. Therefore, many large companies are committed to improving the existing hydroprocessing catalysts, and do not disconnect and issue better performance hydroprocessing catalysts.
  • the development direction of hydrotreating catalysts is to further reduce the metal content in the catalyst, improve its catalytic activity and change the properties of the catalyst support to make it more suitable for the treatment of inferior oils.
  • Hydrotreating catalysts generally contain a metal and / or metal oxide component with a hydrogenation function and a catalyst support, and some catalysts also contain auxiliary agents.
  • Commonly used metal and / or metal oxide components having a hydrogenation function are selected from Group VI I Group I metals and / or metal oxides and Group VIB metals and / or metal oxides in the periodic table of elements.
  • the Group VI I I metal and / or metal oxide may be one or more of metals and metal oxides such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, and metal oxides.
  • the most commonly used Group VI II metals and / or metal oxides are selected from one or more of nickel, cobalt metal and metal oxides.
  • the Group VIB metal and / or metal oxide may be one or more of chromium, molybdenum, tungsten metal and metal oxide.
  • the most commonly used Group VIB metal and / or metal oxide is selected from molybdenum. , One or more of tungsten metal and metal oxide.
  • auxiliaries are selected from one or more of magnesium oxide, phosphorus oxide and fluorine Species.
  • catalyst supports are silica, alumina and silica-alumina supports.
  • alumina is the most widely used catalyst support.
  • the alumina sol is dried and fired to obtain a carrier having a pore volume of 0.15 to 0.45 ml / g, and then impregnated with tungsten, nickel, and dried and fired to obtain nickel oxide containing 10 to 18 % Wt, 25-40wt% tungsten oxide and 1-9wt% fluorine catalyst. Due to the excessive metal content, especially the nickel content, the catalyst cost is too high.
  • US 4, 330, 395 uses tungsten compound and aluminum compound as raw materials, prepares a distillate hydrorefining catalyst by evaporating to dry, roasting, impregnating with nickel compound, and then sulfurizing and fluorinating with sulfur compound and fluorine compound.
  • This catalyst also has the disadvantage of excessively high metal content, and its preparation method is also relatively complicated.
  • CN 85, 104, 438 B High-purity boehmite prepared by the method of hydrolyzing aluminum alkoxide or alkyl aluminum as a precursor of a catalyst carrier, and preparing a nickel oxide containing 1 to 5 wt% of nickel oxide and tungsten oxide 12 35% by weight and 1-9% by weight fluorine refining catalyst.
  • this catalyst has a low metal content, it is one of the most highly refined distillate hydrorefining catalysts in the prior art.
  • the precursor of the catalyst carrier is a relatively expensive alkoxyaluminum or a high-purity boehmite prepared by the hydrolysis method of an alkylaluminum, the cost of the catalyst is relatively high.
  • CN1, 169, 336A discloses a distillate hydrorefining catalyst and a preparation method thereof.
  • the catalyst composition is nickel oxide 1 to 5 wt%, tungsten oxide 12 35 wt%, fluorine 1 to 9 wt%, and the rest is alumina.
  • the alumina is compounded by one or more small-pore alumina and one or more large-pore alumina in a weight ratio of 75:25 to 50:50.
  • small-pore alumina refers to alumina whose pore volume is less than 80 angstroms and the pore volume accounts for more than 95% of the total pore volume
  • large-pore alumina refers to a pore volume whose pore diameter is 60-600 angstroms and the pore volume accounts for more than 70% Alumina.
  • the preparation method of the catalyst includes forming and preliminarily immersing an alumina precursor with a fluorine-containing aqueous solution and a nickel-tungsten precursor aqueous solution in order, and drying and firing after each impregnation, wherein the alumina precursor has a pore diameter smaller than 80 Angstrom pore volume accounts for more than 95% of the total pore volume.
  • Precursors of small pores alumina and pore diameter 60-600 Angstrom pore volume accounts for 70.
  • the alumina carrier of the catalyst prepared according to this method the pore volume with a pore diameter of 40 to 100 Angstroms can account for more than 75% of the total pore volume.
  • This catalyst is also added in the prior art.
  • One of the catalysts for hydrogenation of distillates with the highest hydrogen activity since the catalyst uses two types of alumina, its preparation method is relatively complicated.
  • CN 1, 105, 053A discloses a catalyst suitable for hydrorefining of heavy distillates.
  • the composition of the catalyst is 1 to 5% of nickel oxide and 15 to 38 weight of tungsten oxide. /.
  • Fluorine is 1 to 9% by weight
  • its carrier is a modified alumina obtained by air and water vapor treatment at high temperature.
  • the pore distribution of the modified alumina is concentrated within the range of 60 200 Angstroms. In the step of processing steam at high temperature, this method obviously has the disadvantages of complicated preparation process and high energy consumption.
  • ⁇ -alumina is a commonly used catalyst support or substrate.
  • ⁇ -alumina is used as the support or matrix of the catalyst, its properties play a very important role in the performance of the entire catalyst.
  • the crystallinity of pseudo-boehmite is required to be high.
  • the alumina trihydrate heterocrystals should be low, preferably not.
  • the content of impurity ions should be low.
  • the content of acid ions in alumina products, such as sparse acid ions, is not more than 2% by weight, and the content of alkali metal oxides is not more than 0.15% by weight.
  • the rhenium-alumina support formed after the quasi-boehmite is calcined should have a large specific surface, high strength, and moderate pore volume. At the same time, it should have a concentrated pore distribution.
  • pseudo-boehmite and thorium-alumina a commonly used method for preparing pseudo-boehmite and thorium-alumina is the sodium metaaluminate (or sodium aluminate) -aluminum sulphate (aluminum nitrate, aluminum trichloride, nitric acid, or sulfuric acid) method. .
  • US2,980,632 discloses a method for preparing an alumina-based catalyst, which method comprises precipitating hydrated alumina from an aqueous solution of an aluminum compound at a pH value of 7 to 9.5, and at a higher pH value ( 10 ⁇ 11) under the aging slurry at least 0.25 ⁇ 0.5 hour.
  • the hydrated alumina precipitation is obtained by neutralizing a sodium aluminate solution and an aluminum sulfate solution, and the higher pH value is achieved by reducing the amount of aluminum sulfate solution used.
  • the pseudo-boehmite is prepared by this method, since the adjustment of the pH value is achieved by reducing the amount of aluminum sulfate solution, the amount of sodium aluminate is relatively increased.
  • alumina prepared by this method is not suitable as a support for a distillate hydrorefining catalyst.
  • U.S. Patent No. 4,371,513 discloses a method for preparing alumina suitable for forming spherical particles.
  • the method involves precipitating alumina under special and controlled conditions such as reactant concentration, reaction temperature, time, and pH, and filtering at high pH. Specifically, the method includes alumina concentration of 5-9% by weight and temperature of 130-160.
  • F Add a sufficient amount of aluminum sulfate solution to water at a temperature of 140-170 ° F and adjust the pH of the mixture to 25.
  • a sodium aluminate solution having an alumina concentration of 18-22% by weight and a temperature of 130 to 160 ° F and another part of an aluminum sulfate aqueous solution are simultaneously added to the above mixture to precipitate alumina to form an alumina slurry.
  • the pH and temperature were maintained at 7 ⁇ 8 and 140 ⁇ 180 ° F, and the solution was added at a rate to ensure the formation of intermediate boehmite and boehmite.
  • the pH of the slurry was adjusted to 9.5 to 10.5, the slurry was filtered, and the filter cake was washed to obtain substantially pure aluminum hydroxide.
  • the pores of the alumina prepared by this method are distributed over a wide range (with a pore diameter ranging from 100 to 1000 angstroms), and the pore distribution is not concentrated. Not suitable as a carrier for distillate hydrorefining catalysts.
  • US 4,248,852 discloses a method for preparing alumina as a catalyst support.
  • the method includes establishing at least one aluminum hydroxide seed gel having a pH of 6-10. Add (a) an aluminum compound in order to adjust the pH of the sol to less than 5 or greater than 11 to dissolve the aluminum hydroxide crystals, and (b) a neutralizing agent to bring the pH back to 6 to 10 to hydrate Alumina crystals grow. Then, the aluminum compound and the neutralizing agent are added at least twice more to make the hydrated alumina crystal continue to grow. The hydrated alumina crystals are dried and fired.
  • the alumina prepared by this method has a large specific surface and a pore volume controlled within a certain range (0.5-2 ml / g). And the pores are concentrated in the range of pore diameters from 0 to 200 or 100 to 500 angstroms. However, this method uses a method of shaking the pH at least three times, and the operation is too complicated.
  • GB2, 146, 633A discloses a method for preparing alumina for use as a catalyst support.
  • the method includes (1) under the conditions of pH 6.0 ⁇ 8.5 and temperature 50 ⁇ 65 ", an aluminum sulfate solution and a A sodium aluminate solution was simultaneously added to deionized water to prepare an aqueous slurry containing amorphous hydrated alumina; (2) Aluminate sufficient to neutralize the slurry prepared in the first step was added to the slurry prepared in the first step; Sodium solution to prepare a second aqueous slurry with alumina content of at least 7% by weight, wherein the amount of sodium aluminate used in steps (1) and (2) is equivalent to the equivalent amount of aluminum sulfate in step (1) 0.95 ⁇ 1.05; (3) filter out the amorphous hydrated alumina in the second aqueous slurry, and then wash the filter cake with ammonia solution, nitric acid solution and ammonia solution in order to make the
  • Petroleum Refining 11-12, 50 ⁇ 57, 1978 discloses a method for preparing Y-alumina by the lyo-aluminum-sodium metaaluminate method.
  • the method comprises the following steps: Proportional co-flow is added to the neutralization tank with a stirrer for continuous gelatinization.
  • the gelatinization pH value is controlled at 7.5 ⁇ 9.0
  • the temperature is controlled at 40-70X :
  • the residence time is 15 minutes
  • the gelatinized slurry is in the aging tank. Collect, collect for 30 minutes, maintain a certain temperature, age for 30 minutes, and filter. Then, 30 times (weight) of purified water was added to the filter cake for the first wash.
  • the filtration process is always accompanied by filtration and leakage. Therefore, the content of alumina in the filter cake collected during the first washing is always lower than the amount of alumina in the gelation process.
  • multiple filters are generally used at the same time, and the filtration performance of the filters is different, which results in that the alumina collected in the first washing is not only less than the input amount of the gelation process, but also the oxidation collected in different batches.
  • the amount of aluminum Because the amount of sodium carbonate is determined based on the amount of aluminum in the gelatinization process, it is difficult to determine the amount of sodium carbonate, and the industry can only solve it based on estimates, which sometimes differ greatly.
  • the amount of sodium carbonate has a very important effect on the pore volume and pore distribution of alumina. Therefore, the above-mentioned method of adding sodium carbonate makes the performance of the prepared alumina lack repeatability and the performance of the prepared alumina is very unstable. The performance of alumina-made hydrogenation catalysts is also very unstable.
  • the choice of industrial filter is preferably a belt filter, because this filter can be washed at one time, thereby improving the yield of alumina and production efficiency, and reducing costs. Because the above sodium carbonate is added during the washing process, filtering must be performed from aging to the first washing, which limits the use of the belt filter.
  • alumina can be prepared by using sodium metaaluminate solution or sodium aluminate solution produced by bauxite and carbon dioxide exhaust gas as raw materials. Therefore, this method is industrially It is widely used.
  • the gelation reaction (or neutralization reaction) of sodium metaaluminate solution (or sodium aluminate solution) and carbon dioxide can be performed batchwise or continuously.
  • CO 2 gas is passed into a large amount of sodium metaaluminate solution or sodium aluminate solution, and the pH value (endpoint pH value) of the gelation reaction is controlled at 9.5, the best 10 or more.
  • the sodium metaaluminate solution or the sodium aluminate solution and carbon dioxide are each contacted at a certain rate, and the pH value (process pH) of the gelatinization reaction is also controlled at 9.
  • the gelation reaction at this high pH value can obtain pseudo-boehmite (precursor of ⁇ -alumina) with high crystallinity, but because its grain shape is solid spherical, the grains are densely packed, so The alumina produced after firing has smaller pores, The pore diameter between 20 and 60 Angstroms accounts for more than 60% of the total pore volume, which greatly limits its application in distillate hydrorefining catalysts.
  • US 3,268,295 discloses a method for preparing hydrated alumina.
  • the hydrated alumina contains 1.4 to 1.6 moles of crystal water per mole of alumina, and the average grain size is 20 to 40 angstroms.
  • X-ray diffraction spectrum 2 ⁇ 28.
  • the peak area of the peak is 40-90% of the corresponding peak area of boehmite.
  • the method comprises (a) reacting carbon dioxide sodium content of less than about 200 grams per liter Na 2 C0 3 and sodium aluminate stoichiometry prepared substantially free of crystalline aluminum hydroxide amorphous alumina hydrate, the reaction conditions The reaction temperature is 25-60, the reaction time is 2-20 minutes, and the pH value is 10-11.
  • Aluminum hydroxide is precipitated from the neutralization reaction instead of the hydrolysis reaction.
  • B Separate the precipitate from the mother liquor, wash it, and re-slurry the precipitate with water to disperse the precipitate, leaving it in an amorphous state.
  • C Precipitation in the aged slurry at a temperature below 100 ° C and a pH value of 8-9 for 5 to 90 minutes to transform the amorphous aluminum hydroxide into crystalline hydrated aluminum oxide.
  • EP0, 147, 167A2 discloses a method for continuously neutralizing aluminate solution to produce alumina gel, which method comprises (a) flowing a sodium aluminate solution having a certain total causticity and a certain alumina to causticity ratio into A reactor; (b) maintaining the solution in the reactor at a certain temperature; (c) contacting the solution with a neutralizing reagent to lower the pH to a predetermined value, said neutralizing reagent being selected from the group consisting of The gas of the sodium aluminate solution and the liquid insoluble in the sodium aluminate solution; (d) continuously removing the alumina gel produced from the reactor, and according to the causticity, the ratio of alumina to the causticity, and the reaction temperature , PH and residence time, select the removal speed to make the alumina gel form a specific morphology.
  • the PH value of the neutralization reaction can be from 8.5 to 12, for example, when the pH is 8.5 to 10.2, dawsonite can be obtained. Gibbsite can be obtained at a pH of about 12. When the pH is 10.4 to 10.7, pseudo-boehmite will be mainly obtained.
  • CN85, 100, 161A discloses a process for producing pseudo-boehmite by using industrial sodium aluminate solution in the production of alumina through carbonation.
  • the method includes adding distilled water or deionized water to an industrial sodium aluminate solution having an alumina concentration of 70 to 130 g / liter and a temperature of 70 to 100, diluting and cooling to an alumina concentration of 20 to 60 g / liter, and a temperature of 15 to 45 X. :.
  • the diluted and cooled solution was filtered and purified to remove eight (010 3 residues).
  • the slag is then passed through carbon dioxide gas with a concentration of 30-45% for rapid carbonation to form a gel.
  • Carbonated gelatin is divided into two modes: intermittent and continuous.
  • intermittent carbonized gelatin the (: 0 2 gas velocity 2 ⁇ 8 grams C0 2 / grams A1 2 0 3 ⁇ hours, time 10 ⁇ 30 minutes.
  • the gas flow rate (0 2 gas velocity 1 ⁇ 6 C0 2 / g A1 2 0 3 ⁇ hours, the carbonation process is 30-90 minutes.
  • the slurry after gelation is then heated to 70-100, and the temperature is aging 1 -6 hours. Alternatively, perform liquid-solid separation directly and then age in the washing process.
  • the separated solid is washed with distilled water or deionized water at a temperature of 70-100 ⁇ 1 to 4 times, and the washing liquid part is returned for dilution industry. For the use of sodium aluminate solution. The separated mother liquor and the remaining washing solution are sent back to the alumina production process. Finally, the washed wet material is processed by conventional drying and crushing methods to obtain powdered pseudoboehmite. According to the application 5 ⁇ 12. 0 ⁇ The gelling conditions, the endpoint pH value or process pH value is also controlled between 10. 5 ⁇ 12. 0.
  • US 4,500,444 discloses a method of basic aluminum carbonate colloid, which method comprises reacting sodium metaaluminate with carbon dioxide in an aqueous solution having a pH of 6.8 ⁇ 0.2 and a temperature of 10-to form an alkali Colloidal aluminum carbonate, filtered, and separated from the reaction medium.
  • the colloid can be formed into pseudo-boehmite after acid hydrolysis.
  • the pseudo-boehmite prepared by this method the sulphate and sodium ion contents are significantly reduced.
  • the quasi-boehmite has low crystallinity, pore volume and pore size, and is not suitable as a carrier for distillate hydrogenation catalysts.
  • the catalyst provided by the present invention comprises an alumina support and at least one Group VIB metal and / or oxide and at least one Group VIII metal and / or oxide supported on the alumina support; the alumina
  • the pore volume of the carrier is not less than 0.35 ml / g, and the pore volume with a pore diameter of 40-100 Angstroms accounts for more than 80% of the total pore volume. It is prepared by one or two of the following methods:
  • Method 1 includes contacting a solution of sodium metaaluminate or sodium aluminate with one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, nitric acid, and sparse acid solution, and performing a gel formation reaction.
  • the gel formation reaction may be continuous
  • the method is carried out by aging the obtained aluminum hydroxide, separating the solid and liquid, washing, drying, and baking the obtained solid product.
  • the pH value of the primary gelation reaction is 6 to 9. 5
  • the temperature of the gelation reaction is 10 to 100 "
  • the slurry generated by the gelation reaction (primary gelation) is collected in the secondary gelatinization tank and collected. The time is not less than 10 minutes.
  • the slurry is switched to another secondary gelling tank to continue collecting.
  • the alkali metal carbonate and the alkali metal hydrogen carbonate are added.
  • the pH value of the secondary gelatinization is controlled at 9. 0 ⁇ 10. 5.
  • the concentration of the sodium metaaluminate or sodium aluminate solution and the concentration of the aluminum phosphite, aluminum nitrate, aluminum chloride, nitric acid, and sulfuric acid solutions may be arbitrary and possible concentrations, as long as the gelation reaction is guaranteed once.
  • the pH value is 6 ⁇ 9.5.
  • the concentration of sodium metaaluminate or sodium aluminate solution is preferably 30-300 g of alumina / liter, and the concentration of aluminum sulfate, aluminum nitrate and aluminum chloride is preferably 10 to 120 g.
  • the concentration of alumina / liter, nitric acid and osmic acid solutions is preferably 5 to 15% by weight.
  • the sodium carbonate, ammonium carbonate, and ammonium bicarbonate may be added in the form of a solid or in the form of an aqueous solution, and preferably in the form of an aqueous solution.
  • the pH value of the primary gelation reaction is preferably 6-9.
  • the temperature of the primary gelation reaction is preferably 30 to 90 t :.
  • the collection time is preferably 10 to 90 minutes.
  • the pH of the secondary stranding is preferably 9.5 to 10.5.
  • the solid-liquid separation method may be a conventional method, such as a filtration method or a centrifugation method.
  • the aging is performed according to conventional conditions. Generally, the aging temperature is 5 to 100C, preferably 30 to 100, more preferably 30 to 90, and the aging time is greater than 0.5 hours, preferably 1 to 8 hours.
  • the washing is performed according to a conventional method.
  • the purpose of the washing is to remove impurity ions, such as sulfate ions, sodium ions, etc.
  • the washing should make the content of the alkali metal oxide in the formed alumina not more than 0.15% by weight.
  • the content of root ions is not more than 2
  • the molding method can adopt various existing methods, such as a tablet molding method, a ball forming method, and an extrusion molding method, and the extrusion molding method is preferably adopted.
  • Various existing peptizers and / or extrusion aids can be added during the molding process.
  • the peptizing agent may be various inorganic or organic acids, such as hydrochloric acid, nitric acid, citric acid, acetic acid, and the like.
  • the extrusion aid may be a starch-based substance, a cellulose-based substance, or the like.
  • the drying conditions are conventional drying conditions, and the drying temperature may be from room temperature to below the pseudo-boehmite crystal transition temperature, preferably 100-200 ° C.
  • the roasting conditions are conventional roasting conditions.
  • the roasting temperature is 500-900C, preferably 550 ⁇ 850X
  • the roasting time is 2 ⁇ 8 hours, preferably 3 ⁇ 6 hours.
  • Method 2 includes contacting a solution of sodium metaaluminate or sodium aluminate with a carbon dioxide-containing gas, forming a batch in a continuous or continuous manner, aging the obtained aluminum hydroxide, separating the solid from the liquid, washing, drying, and roasting the obtained solid product.
  • the gelation end point ⁇ ⁇ value or pH control within the range of 6 to 9.5, gelation of the reaction time or residence time less than 40 minutes at a temperature of 10-100 gelation reaction ", gel-forming reaction After the end, quickly add an alkaline substance to raise the pH of the slurry to above 9.5 or quickly perform solid-liquid separation and wash coating.
  • the concentration of the sodium metaaluminate or sodium aluminate solution may be any arbitrary concentration that may exist.
  • the concentration of the sodium metaaluminate or sodium aluminate solution is preferably 5 to 200 g of alumina / liter, more preferably 5 to 120 g of alumina / liter.
  • the carbon dioxide-containing gas may be pure carbon dioxide gas, or a mixed gas composed of carbon dioxide and an inert gas that does not affect the reaction, such as one or more kinds of gases such as air, nitrogen, helium, and argon.
  • a mixture of carbon dioxide such as one or more kinds of gases such as air, nitrogen, helium, and argon.
  • the content of carbon dioxide in the carbon dioxide-containing gas can vary within a wide range. In general, the content of carbon dioxide is not less than 5% by volume, and preferably not less than 20% by volume.
  • the gelation reaction may be batch-type.
  • the reaction temperature is controlled at 10-100 ⁇ , preferably 10 80 :
  • the endpoint PH value is controlled at 6-9. 5 and preferably 6. 5 9.3.
  • the gelation reaction time does not exceed 40 minutes, and preferably does not exceed 30 minutes.
  • an alkaline substance is added quickly, so that the PH value of the slurry rapidly rises above 9.5, preferably between 9.5 and 11.5, or the solid-liquid separation and washing are performed quickly. It is then aged, filtered, washed, and dried under normal conditions to obtain pseudo-boehmite, which forms an alumina support after firing.
  • the gelation reaction may also be continuous.
  • this gelation method firstly, deionized water is pre-added in a gelatinization tank, and at the same time, a gas containing carbon dioxide is passed from the bottom of the tank and a sodium metaaluminate or sodium aluminate solution is passed from the top of the tank.
  • the sodium metaaluminate or sodium aluminate solution is brought into countercurrent contact with the carbon dioxide-containing gas, and the gelatinization temperature is controlled from 10 to 100, preferably from 10 to 80 X.
  • the concentration and flow rate of the sodium metaaluminate or sodium aluminate solution and the carbon dioxide-containing gas are controlled.
  • the concentration and flow rate make the pH value of the gelation process between 6 and 9.5, preferably between 6.5 and 9.3, and the residence time does not exceed 40 minutes, and preferably does not exceed 30 minutes.
  • the slurry generated during the gelatinization process is continuously or intermittently collected into an aging tank, and the alkaline substance is continuously or intermittently added to increase the pH of the slurry to above 9.5, preferably between 9.5 and 11.5. After collecting for a period of time, the slurry generated by the gelation reaction is switched to another aging tank, and the slurry with a pH value greater than 9.5 in the first aging tank is aged, filtered, washed and dried to obtain pseudo-boehmite, Alumina support was obtained after firing.
  • the basic substance is selected from one or more of an inorganic base, an organic base, and an aqueous solution thereof.
  • the inorganic base is preferably one or more of alkali metal hydroxides, metaaluminates, carbonates, bicarbonates, ammonium carbonate, ammonia, and aqueous solutions thereof.
  • the organic base is preferably one or more of water-soluble amines, urea, pyridine and their aqueous solutions, preferably one of water-soluble aliphatic amines, hydrocarbyl ammonium hydroxide, urea, pyridine and their aqueous solutions.
  • Species or species in particular methylamine, ethylamine, propylamine, propylenediamine, various isomers of butylamine, various isomers of pentylamine, tetraethylammonium hydroxide, urea, acne and their One or more of the aqueous solutions.
  • the solid-liquid separation method may be a filtration method or a centrifugation method.
  • the rapid washing after solid-liquid separation is performed to remove sodium bicarbonate, a reactant capable of forming schistite, and it is generally washed at least once with deionized water not less than 10 times the weight of the solid product.
  • the aging is performed according to conventional conditions. Generally, the aging temperature is 5 to 100 C, preferably 30 to 100 "C, more preferably 50 100, and the aging time is greater than 0.5 hours, preferably 1 to 8 hours.
  • the aging medium may be mother liquor or deionized water. When the method of rapid solid-liquid separation is adopted, the aging medium is generally deionized water.
  • the washing after aging is performed according to a conventional method, the purpose of washing is to remove impurity ions therein, so that the content of alkali metal oxide therein is less than 0.15 wt%.
  • the drying conditions are conventional drying conditions, and the drying temperature may be from room temperature to below the pseudo-boehmite transition temperature, preferably 100-200X.
  • the roasting conditions are conventional roasting conditions, such as a firing temperature of 500 to 900 C, preferably 550 to 850 ", and a firing time of 2 to 8 hours, preferably 36 hours.
  • the Group VIB metal and / or oxide refers to one or more of chromium, molybdenum, tungsten metal, and their oxides, and is preferably molybdenum, tungsten metal, and their oxides. One or more of them are more preferably tungsten and / or an oxide thereof.
  • the content of the Group VIB metal is from 12 to 35% by weight based on the oxide.
  • the Group VIII metal and / or oxide refers to One or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum metal and their oxides, preferably one or more of cobalt, nickel metal and their oxides, More preferred is nickel and / or an oxide thereof.
  • the content of the Group VI and II metal is 1 to 5 wt% based on the total amount of the catalyst and based on the oxide.
  • the catalyst provided by the present invention may also and preferably contain 1 to 9% by weight of fluorine.
  • the preparation method of the catalyst provided by the present invention includes impregnating a catalyst support with an aqueous solution containing Group VIB and Group VIII metals, drying and baking after impregnation, wherein the catalyst support is the alumina support prepared by Method 1 and / or Method 2.
  • the aqueous solution containing Group VIB and Group VI II metals refers to an aqueous solution containing Group VIB and Group VI II metal compounds.
  • an aqueous solution containing molybdenum and / or tungsten and nickel and / or cobalt compounds is preferred, such as One or more of ammonium tungstate, ammonium tungstate, ethylammonium metatungstate, ammonium molybdate and one or more of nickel metatungstate, nickel nitrate, nickel acetate, cobalt nitrate, cobalt acetate Mixed aqueous solution.
  • aqueous solution containing tungsten and a nickel compound such as one or more of ammonium metatungstate, ammonium tungstate, and ethyl ammonium metatungstate, and one of nickel metatungstate, nickel nitrate, and nickel acetate. Or several mixed aqueous solutions.
  • the fluorine-containing aqueous solution refers to an aqueous solution of a fluorine-containing inorganic compound, such as an aqueous solution of ammonium fluoride and / or hydrogen fluoride.
  • the drying of the catalyst support with an aqueous solution containing Group VIB and Group VI II metals or the impregnation of the catalyst support with a fluorine-containing aqueous solution are conventional drying conditions, and the drying temperature may be from room temperature to 300, preferably 100 to 200.
  • the calcination temperature of the catalyst support is impregnated with an aqueous solution containing Group VIB and Group VI II metals or the catalyst support is impregnated with a fluorine-containing aqueous solution.
  • the calcination temperature is 400 to 600 TC, and the calcination time is 1 to 8 hours, preferably 25 hours.
  • the addition of an alkali metal carbonate, a mixed solution of an alkali metal bicarbonate and ammonia water, and addition of ammonium bicarbonate and ammonium carbonate can be completed before aging and filtration.
  • Ammonium bicarbonate and ammonium carbonate overcome the shortcomings of the difficulty in controlling the sodium carbonate in the prior art method of adding sodium carbonate in the washing process.
  • the precursor of alumina prepared using the method 1 provided by the present invention is fibrous boehmite, and the prepared alumina carrier not only has a pore volume of 0.45-0.775 ml / g, and a pore diameter between 40 ⁇
  • the pore volume of 100 angstroms accounts for more than 80% of the total pore volume, and the repeatability is good.
  • the obtained alumina carrier has very uniform properties and stable and reliable quality.
  • the alumina is particularly suitable as a support for a distillate hydrorefining catalyst.
  • the inventors of the present invention have discovered that during the gelation reaction of sodium metaaluminate or sodium aluminate and carbon dioxide, when the end point or process pH value is less than 9.5, it may be accompanied by the interaction of sodium carbonate and aluminum hydroxide to form silk.
  • the reaction of sodalite however, the reaction requires sufficient time to complete. This time generally takes 40 minutes or longer.
  • the gelling pH is less than 9.5, as long as the low pH time is not exceeded. In 40 minutes, a pseudo-boehmite with essentially no silk falconite was obtained.
  • the generated aluminum hydroxide needs to be aged, and the aging time is generally greater than 0.5 hours, plus the gelation time, it must be more than 40 minutes.
  • Method 2 overcomes the quasi-boehmite grains prepared by the prior art sodium meta-aluminate or sodium aluminate-carbon dioxide method, which are solid spherical, and the grains are densely packed. Small disadvantages.
  • the quasi-boehmite prepared by method 2 is fibrous, and the pore volume of the alumina carrier formed after firing is 0.45-0.75 ml / g, and the pore volume of the pores with a pore diameter between 40 and 100 Angstroms accounts for the total pores. With a capacity of more than 80%, this kind of shielded alumina support is particularly suitable for use as a catalyst support for distillate hydrorefining.
  • the catalyst provided by the present invention has higher catalytic activity than the prior art. For example, its desulfurization, denitrification, and aromatic hydrocarbon saturation hydrogenation activities are higher than the catalysts disclosed in CN 85104438 B, and when the catalyst provided by the present invention is used for hydrorefining of high-sulfur inferior shield distillates, Catalytic activity.
  • the catalyst provided by the present invention still has higher hydrodesulfurization, denitrification, and aromatic saturation performance than CN 85104438 B in the case of a low bulk ratio (packing density) (0.88-0.88 g / ml).
  • the corresponding activity of the disclosed catalyst (its bulk ratio is> 1.0 g / liter), that is, the catalyst provided by the present invention still has a higher space velocity Higher hydrogenation activity.
  • the catalyst provided by the present invention also maintains the advantage of lower metal content of the catalyst disclosed in CN 85104438 B. Not only that, the cost of the alumina support prepared by the method 1 and method 2 of the present invention is very low, and its cost is only 15 50% of the cost of the support used in CN 85104438 B. Therefore, the cost of the catalyst provided by the present invention is also greatly reduced.
  • the catalyst provided by the present invention is a catalyst with high activity and low cost, and has great industrial application value.
  • the alumina carrier provided by the present invention is particularly suitable as a carrier or substrate for a distillate hydrocracking catalyst, in addition to being particularly suitable as a carrier for distillate hydrofining catalysts.
  • the catalyst provided by the present invention is particularly suitable for the hydrorefining of petroleum distillates with a distillation range of 80-550X.
  • the catalyst provided by the present invention and the hydrocracking catalyst can be used for the hydrogenation and upgrading of heavy distillates, especially Medium pressure hydrogenation modification process.
  • reaction temperature 200 to 500, preferably 300-reaction pressure.
  • FIG. 1 is a transmission electron microscope photograph of pseudoboehmite, the precursor of the alumina support provided by the present invention.
  • Fig. 2 is a transmission electron microscope photograph of a pseudo-boehmite of the prior art.
  • Fig. 3 is a transmission electron micrograph of pseudo-boehmite, the precursor of the alumina support provided by the present invention.
  • Fig. 4 is a transmission electron microscope photograph of a pseudo-boehmite of the prior art.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • a 250-liter alumina / liter NaA10 2 solution and a 100-gram alumina / liter A1 2 (S0 4 ) 3 solution were simultaneously added to a 2-liter gelling tank (a Secondary gelling tank), the tank was pre-filled with 1.5 liters of water, the flow rate of the NaA10 2 solution was 1.1 liters / hour, and the flow rate of the Al 2 (S0 4 ) 3 solution was adjusted so that the gelation pH was 8. 0, The temperature of the gelatinization process is 50 ° C.
  • the gelatinized slurry is collected in a secondary gelatinization tank (secondary tank). After collecting for 20 minutes, the slurry is switched to another secondary tank for collection.
  • Fig. 1 shows a transmission electron microscope photograph of quasi-boehmite magnified 50,000 times. From its transmission electron microscope picture, the pseudo-boehmite is fibrous. The obtained quasi-boehmite was ground, and according to the conventional conditions for extrusion, water, peptizer nitric acid and starch for extrusion were added to extrude into a three-leaf bar with a diameter of 1.4 mm. Bake at X and bake at 550 for 5 hours. The properties of the alumina support are shown in Table 1.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the concentration of the & 8 10 2 solution in Example 1 was changed to 50 g of alumina / liter, the flow rate was changed to 5.3 l / hour, and the concentration of the A1 2 (S0 4 ) 3 solution was changed to 30 g of alumina / liter, and adjusted Its flow rate makes the gelled PH value of 8.0, and other conditions remain unchanged.
  • the obtained alumina support A 2 has the properties shown in Table 1.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 1 The flow rate of the A1 2 (S0 4 ) 3 solution in Example 1 was adjusted so that the gelling pH value was 6.5, and other conditions were unchanged to obtain the alumina support A 3 , whose properties are shown in Table 1.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 1 The flow rate of the A1 2 (S0 4 ) 3 solution in Example 1 was adjusted so that the gelling pH value was 9.0, and other conditions were unchanged to obtain an alumina support A 4 whose properties are shown in Table 1.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 6 The gelatinization temperature in Example 1 was changed to 75 ° C, and the flow rate of the A1 2 (S0 4 ) 3 solution was adjusted so that the gelatinization pH value was maintained at 8. 0, and other conditions were not changed to obtain an alumina carrier A 5 having properties as shown in Table 1. As shown.
  • Example 6 The gelatinization temperature in Example 1 was changed to 75 ° C, and the flow rate of the A1 2 (S0 4 ) 3 solution was adjusted so that the gelatinization pH value was maintained at 8. 0, and other conditions were not changed to obtain an alumina carrier A 5 having properties as shown in Table 1. As shown. Example 6
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 1 The collection time of the slurry in Example 1 was changed to 80 minutes, and other conditions were not changed to obtain the alumina support A 6 , whose properties are shown in Table 1.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 2 The A1 2 (S0 4 ) 3 solution in Example 1 was changed to an A1 (N0 3 ) 3 solution with the same alumina content, and other conditions remained unchanged to obtain an alumina support 8 7 , whose properties are shown in Table 2.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 2 The A1 2 (S0 4 ) 3 solution in Example 1 was changed to an A1C1 3 solution with the same alumina content, and other conditions remained unchanged to obtain an alumina support A 8 , whose properties are shown in Table 2.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 2 The A1 2 (S0 4 ) 3 solution in Example 1 was changed to sulfuric acid with a concentration of 5% by weight, and other conditions remained unchanged to obtain an alumina carrier A 9.
  • the properties are shown in Table 2.
  • Example 2 illustrates the alumina support provided by the present invention and its preparation.
  • the A1 2 (S0 4 ) 3 solution in Example 1 was changed to nitric acid with a concentration of 7% by weight, and other conditions remained unchanged to obtain an alumina support A 1 () .
  • the properties are shown in Table 2.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 1 Of Example 1 into a mixed solution of sodium bicarbonate and aqueous ammonia, wherein the concentration of ammonium bicarbonate was 50 g / L, ammonia concentration of 5 weight%, P H value of 9.5 adjusted, the other conditions are not
  • the obtained properties are shown in Table 2 below.
  • This example illustrates the alumina plant provided by the present invention and its preparation.
  • Example 2 The sodium carbonate in Example 1 was replaced with an ammonium carbonate solution having a concentration of 50 g / liter, and the pH value of the slurry was adjusted to 9.5, and other conditions remained unchanged to obtain an alumina carrier A 12 whose properties are shown in Table 2.
  • Alumina support was prepared according to the method disclosed in GB2, 146, 633A.
  • the alumina carrier was prepared according to the method of Example 1, except that 0.37 liters of the sodium metaaluminate solution described in Example 1 was added to the slurry collected for 20 minutes, filtered, and washed sequentially with an aqueous ammonia solution, a nitric acid solution, and an aqueous ammonia solution. Filter cake so that the final pH of the filter cake is 10. The filter cake was squeezed and dehydrated to increase the alumina content to 30% by weight, and the dehydrated filter cake was kneaded, extruded, dried, and fired according to the method described in Example 1.
  • FIG. 2 shows a transmission electron microscope photograph of a pseudo-boehmite magnified 50,000 times obtained after kneading and drying the filter cake. From the transmission electron microscope photograph, the pseudo-boehmite is granular.
  • Alumina support was prepared according to the method disclosed in US 2,980,632.
  • the alumina support was prepared according to the method of Example 1, except that the flow of aluminum sulfate was reduced after collecting the slurry for 20 minutes, so that the pH of the slurry was increased to 10.0, and the reference alumina support AB 2 was obtained .
  • the physical and chemical properties of AB 2 are listed in Table 3. Table 2
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina support was prepared according to the method of Example 13, except that the basic substance sodium hydroxide was used instead of the basic substance sodium carbonate solution, and the pH of the slurry was raised to 9.8 within 1 minute to obtain an alumina carrier A 14 .
  • Table 4 shows the physical and chemical properties of A 14 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Alumina support was prepared according to the method of Example 13, except that the basic substance potassium hydroxide was used instead of the basic substance sodium carbonate solution, and the slurry pH was raised to 9.8 in 3 minutes to obtain an alumina carrier A15 .
  • Table 4 shows the physical and chemical properties of A 15 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Alumina support was prepared according to the method of Example 13, except that the alkaline substance sodium carbonate solution was replaced with 2% by weight ammonia water, and the pH of the slurry was raised to 9.8 within 7 minutes to obtain alumina support A 16 .
  • Table 4 shows the physical and chemical properties of A 16 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina carrier was prepared according to the method of Example 13, except that the alkaline substance ammonium carbonate was used instead of the alkaline sodium dong carbonate solution, and the pH of the slurry was raised to 9.5 in 9 minutes. .
  • Table 4 shows the physical and chemical properties of A 17 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Example 2 The temperature was raised to 90 ⁇ , aged for 45 minutes, filtered, washed four times with 20 times deionized water, dried by HO, extruded into strips according to the method of Example 1, dried and calcined to obtain alumina carrier A 18 .
  • Table 5 shows the physical and chemical properties of A 18 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina plant was prepared according to the method of Example 18, except that the concentration of the sodium metaaluminate solution was 80 g of alumina / liter, and the gelation reaction was stopped when the pH dropped to 9.3 after 20 minutes of reaction to obtain alumina.
  • Carrier A 19 Table 5 shows the physical and chemical properties of A 19 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina plant was prepared according to the method of Example 18, except that the concentration of the sodium metaaluminate solution was 40 g of alumina / liter, the initial temperature of the reaction was 30, and the pH dropped to 7.8 after 12 minutes of the reaction. The temperature is 45 X. The amount of sodium carbonate added makes the PH value of the slurry at 7 points The clock rose to 10.20. Aging temperature 80 ", aging time 30 minutes, alumina support A 2 was obtained. Table 5 shows the physical and chemical properties of A 2 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Alumina was prepared according to the method of Example 18, except that the aging temperature was 33 and the temperature of deionized water for washing was 33 C to obtain alumina support A 21 .
  • Table 5 shows the physical and chemical properties of A 21 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the valve at the bottom of the gelling tank is opened, so that the generated slurry flows into a pre-filled 200 ml temperature 35
  • the outflow speed makes the liquid level in the gelling tank neither rise nor fall.
  • a sodium carbonate solution of an alkaline substance having a concentration of 50 g / L was added, and the pH value of the slurry in the aging tank was adjusted to be maintained at 10. ⁇ 0.1, and the temperature was maintained at 40 ⁇ 2.
  • switch the gelled slurry to In the same aging tank, the alkaline substance sodium carbonate solution was switched into the aging tank at the same time.
  • the slurry in the first aging tank was aged at a temperature of 40 ⁇ 2 for 4 hours, filtered, washed twice with 20 times 90 ⁇ deionized water, dried at 120, and extruded and dried as described in Example 1. After baking at 600 ⁇ for 4 hours, an alumina carrier A 22 was obtained. Table 6 shows the physical properties of ⁇ 22.
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina carrier was prepared according to the method of Example 22, except that the temperature of the gelation reaction was controlled to 65 ⁇ 2 ⁇ , and the temperature in the aging tank was 65 when the slurry generated from the gelation reaction was collected. The soil aging temperature was 75 ⁇ 2 to obtain alumina. Carrier A 23 . Table 6 shows the physical and chemical properties of A 23 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • the alumina carrier was prepared according to the method of Example 22, except that the concentration of the sodium metaaluminate solution for the gelation reaction was 50 g alumina / liter, the flow rate was 24 ml / min, and the carbon dioxide concentration in the mixed gas was 75% by volume. At 0.33 m 3 / h, an alumina carrier A 24 was obtained. Table 6 shows the physical and chemical properties of A 24 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Alumina was prepared according to the method of Example 22, except that the flow rate of the mixed gas was 0.85 m 3 / hour, the process pH was 7.0 ⁇ 0.2, and the flow rate of the sodium carbonate solution as an alkaline substance was 30 ml. / Minute to obtain alumina support A 25 .
  • Table 6 shows the physical and chemical properties of A 25 .
  • This example illustrates the alumina support provided by the present invention and its preparation.
  • Alumina was prepared according to the method of Example 13. The difference was that no alkaline substance was added after the gelation reaction was completed, but the filter cake was quickly filtered. The filter cake was washed twice with 20 ⁇ 90 ⁇ deionized water. 10 times deionized water was mixed. After aging for 4 hours, filtration was performed. The other conditions were the same as in Example 13 to obtain alumina A 26. Table 6 shows the physical and chemical properties of A 26 .
  • the gelation reaction end point ⁇ value of Comparative Example 3 was reduced to 8.5, the reaction time was 55 minutes, and other conditions were not changed.
  • the dried product was analyzed by X-ray diffraction to be sodium aluminate (NaAl (0H) 2 C0 3 ), Formed according to the method described in Example 1, dried and calcined to obtain a reference alumina carrier AB 4 , and its physical and chemical properties are listed in Table 7.
  • Example 22 Preparation of reference alumina support.
  • the alkaline substance sodium metaaluminate was not added to adjust the pH value of the slurry, and other conditions remained unchanged.
  • the dried product was analyzed by X-ray diffraction to be gibbsite, formed according to the method described in Example 1, dried and roasted.
  • the reference alumina support AB 5 was obtained , and its physical and chemical properties are listed in Table 7.
  • the alumina support was prepared according to the method of Example 22, except that the flow rate of the mixed gas was 0.45 m 3 / hour, and the process pH was controlled at 10.5 ⁇ 0.1, without adding an alkaline substance sodium carbonate solution to obtain oxidation.
  • Aluminum carrier AB 6 The physical and chemical properties of AB 6 are listed in Table 7.
  • Example 1 10 The aluminum oxides A-Ai prepared in Example 1 10 were weighed separately.
  • 200 g of alumina ⁇ ⁇ prepared in Example 11 was taken and immersed in 200 ml of a 3.47 wt% ammonium fluoride solution for 1 hour.
  • alumina A 7 after immersion in fluorine, and use a mixed solution containing 35.0 g / ml of tungsten oxide and 2.78 g / ml of nickel oxide, a mixed solution of ammonium metatungstate and nickel nitrate 180 mM. Liters for 2 hours.
  • Alumina A 8 after roasting with fluorine was immersed, and immersed in 180 ml of a mixed solution of ammonium metatungstate and nickel nitrate containing 35.0 g / ml of tungsten oxide and 5.55 g / ml of nickel oxide for 2 hours.
  • Alumina A 9 after roasting with fluorine was immersed, and immersed in 180 ml of a mixed solution of ammonium metatungstate and nickel nitrate containing 22.2 g / ml of tungsten oxide and 3.61 g / ml of nickel oxide for 2 hours. Take alumina impregnated alumina A 1 () and immerse it in 180 ml of a mixed solution containing 43.0 g / ml of tungsten oxide and 3.61 g / ml of nickel oxide for 180 hours.
  • the catalyst was prepared according to the method described in Example 27, except that the alumina support used was the alumina carriers 8 8 1 and AB 2 prepared in Comparative Examples 1 and 2, respectively, and the obtained reference catalysts were numbered ⁇ and ⁇ , 8 1
  • the total tungsten oxide, nickel oxide, and fluorine contents are listed in Table 12.
  • the catalyst was prepared according to the method described in Example 27, except that the alumina support used was alumina supports 8 3 and AB 6 prepared in Comparative Examples 3 and 6, respectively.
  • the reference catalysts obtained were numbered ⁇ and ⁇ , and 8 3 and The contents of tungsten oxide, nickel oxide and fluorine are listed in Table 12.
  • Example 27 A catalyst was prepared according to the method, except that the alumina support CN 85104438B in Example 2 using the alumina carrier is used, the catalyst obtained number of reference B 5. The contents of tungsten oxide, nickel oxide and fluorine of B 5 are listed in Table 12. Table 8
  • Nickel oxide content weight 2.3
  • Example No. 33 34 35 36 37 38 Support No. A 7 A 8 A 9 Aio A u A 12 Catalyst c 7 c 8 c 9 Cio C n C 2 Tungsten oxide content, weight% 23. 6 23. 6 15. 0 30 0 23. 6 23. 6 Nickel oxide content,% by weight 2. 0 4. 0 2. 6 2. 6 2. 6 2. 6 2. 6 Fluorine content,% by weight 4. 5 4. 5 4. 5 4. 5 2 3 7. 0 Specific surface, m 2 / g 164 168 165 160 159 158 Pore volume, ml / g 0.54 0. 42 0. 52 0. 41 0. 57 Heap ratio, g / ml 0.80 0. 85 0. 81 0. 85 0. 79 0. 79
  • Example number 39 40 41 42 43 44 45 Support number used Ai3 A 14 A 15 Ai6 A 17 Ai8 ⁇ 19 Catalyst ⁇ 13 c 14 c 15 Ci6 C 17 Ci8 ⁇ 19 Tungsten oxide content, weight 21. 3
  • Nickel oxide content weight 2.3
  • Example number 46 47 48 49 50 51 52 Support number used A 20 ⁇ 21 A22 A 2 3 A 24 A 2 5 A 2 6 Catalyst C20 ⁇ 21 C22 C23 C25 ⁇ 26 Tungsten oxide content, weight% 21. 3
  • the obtained strip-shaped catalysts ( ⁇ -( 26 were cut into strips having a length of 2-3 mm, respectively), and their hydrodesulfurization activities were evaluated on a 100-liter fixed-bed hydrogenation reactor using feedstock 1 shown in Table 13.
  • Catalysts The loading capacity is 100 ml (78 ⁇ 86 g), and the reaction conditions are 300 or 3401: reaction pressure, 3.2 MPa, liquid hourly space velocity 3.0 hours-hydrogen oil volume ratio 300, the evaluation results at different reaction temperatures are shown in Table 14. -16 in.
  • Feedstock number Feedstock 1 Feedstock 2 Feedstock name Changerline kerosene catalytic cracking diesel density, g / ml 0.8399 0. 9031 Decomposed content, ppm 11000 2536 Nitrogen content, ppm 58. 4 1901 Basic nitrogen content, ppm 22 402 gum content, 22 mg, 80 milliseconds, 22 44. 4 liters
  • a 100 ml fixed-bed hydrogenation reaction apparatus was evaluated for its hydrodesulfurization and denitrification activity using the stock oil 2 shown in Table 13.
  • the catalyst loading was 100 ml, and the reaction conditions were reaction temperatures of 320 and 350, and the liquid hourly space velocity was 2 hours—the hydrogen-to-oil volume ratio was 350.
  • the evaluation results at different reaction temperatures are listed in Tables 18-20.
  • the catalyst was evaluated on a small fixed-bed reaction apparatus ( 26 toluene saturated hydrogenation activity, the catalyst loading was 1.0 g, and 3% by weight of carbon disulfide cyclohexane was used in a 300 hydrogen atmosphere.
  • the alkane solution is presulfided for 2 hours, and then the reaction raw materials are introduced, the reaction temperature is 360, the pressure is 4.1 MPa, the weight hourly space velocity is 3.4 hours- 1 , the hydrogen oil ratio is 400, and the sample is taken after 3 hours of reaction.
  • the reaction products are analyzed online by gas chromatography. The reaction results are shown in Tables 22-24.
  • Comparative Examples 22 to 26 This example illustrates the toluene hydrogenation performance of the catalyst prepared in the comparative example.
  • Example 105-- 140 different conditions evaluated activity of the catalyst except that the catalyst used as the reference catalyst B 5, the evaluation results are shown in Table 25.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

一种馏分油加氢精制催化剂、 其载体及制备 发明领域
本发明是关于一种馏分油加氢精制催化剂和它的制备方法以及该 催化剂的载体及其制备方法。 更具体地说， 是关于一种含第 VIB 族 金属和 /或金属氧化物和第 VIII族金属和 /或金属氧化物的镏分油加 氢精制催化剂和它的制备方法以及其氧化铝载体及该氧化铝载体的 制备方法。
现有技术描述
近年来， 世界范围内原油劣质化倾向曰益明显， 石油产品中疏、 氮和芳 烃含量日益增高， 显然， 越来越严格的环保要求与这一现 实间的矛盾愈发尖锐。 众所周知， 加氢是改善油品质量最有效的 工艺手段之一， 加氢处理催化剂则是这个工艺中最为重要和关键 的技术。 因此， 许多大公司均致力于对现有加氢处理催化剂的改 进工作， 并不断开发出性能更好的加氢处理催化剂。 加氢处理催 化剂的发展方向是进一步降低催化剂中金属的含量， 提高其催化 活性以及改变催化剂载体的性质使之更适合劣盾油品的加氢处 理。
加氢处理催化剂一般含有具有加氢功能的金属和 /或金属氧化 物組分及催化剂载体， 有些催化剂中还含有助剂。
常用的具有加氢功能的金属和 /或金属氧化物组分选自元素周 期表中第 VI I I族金属和 /或金属氧化物及第 VIB族金属和 /或金属 氧化物。 所述第 VI I I 族金属和 /或金属氧化物如可以是铁、 钴、 镍、 钌、 铑、 钯、 锇、 铱、 铂的金属和金属氧化物中的一种或几 种。 最为常用的第 VI II 族金属和 /或金属氧化物选自镍、 钴金属 和金属氧化物中的一种或几种。 所述第 VIB族金属和 /或金属氧化 物如可以是铬、 钼、 钨的金属和金属氧化物中的一种或几种， 最 为常用的第 VIB族金属和 /或金属氧化物选自钼、 钨金属和金属氧 化物中的一种或几种。
常用的助剂选自镁的氧化物、 磷的氧化物和氟中的一种或几 种。
常用的催化剂载体为氧化硅、 氧化铝及氧化硅-氧化铝载体。 其中， 氧化铝是应用最为广泛的催化剂载体。
US 3, 779, 903 中将氧化铝溶胶干燥并焙烧， 制得孔体积为 0. 15 - 0. 45 毫升 /克 的载体， 然后浸渍钨、 镍并干燥、 焙烧制得 含氧化镍 10 ~ 18 重％ , 氧化钨 25 40 重％和氟 1 - 9 重％的催 化剂， 该催化剂由于金属含量， 特别是镍含量过高， 导致催化剂 成本过高。
US 4, 330, 395 以钨化合物和铝化合物为原料， 通过蒸干、 焙烧、 用镍化合物浸渍， 然后用硫化合物和氟化合物进行硫化和 氟化， 制备出一种馏分油加氢精制催化剂， 这种催化剂同样有金 属含量过高的缺点， 其制备方法也比较复杂。
CN 85, 104， 438 B 采用烷氧基铝或烷基铝水解的方法制备的 高纯一水铝石作为催化剂载体的前身物， 制备出一种含氧化镍 1 ~ 5 重％、 氧化钨 12 35 重％、 氟 1 ~ 9 重％的加氢精制催化剂， 该催化剂虽然具有较低的金属含量， 是现有技术中加氢活性最高 的馏分油加氢精制催化剂之一。 但是， 由于该催化剂载体的前身 物为价格较贵的烷氧基铝或烷基铝水解法制备的高纯一水铝石致 使催化剂成本较高。
CN1 , 169， 336A 公开了一种馏分油加氢精制催化剂及其制备 方法， 该催化剂组成为氧化镍 1 ~ 5 重％ , 氧化钨 12 35 重％, 氟 1 ~ 9 重％ , 其余为氧化铝。 其中， 所述氧化铝是由一种或多种 小孔氧化铝与一种或多种大孔氧化铝按照 75: 25 ~ 50： 50 的重量 比复合而成的。 其中， 小孔氧化铝为孔直径小于 80 埃孔的孔体积 占总孔体积 95 % 以上的氧化铝， 大孔氧化铝为孔直径 60 - 600 埃 孔的孔体积占总孔体积 70 % 以上的氧化铝。 该催化剂的制备方法 包括将氧化铝前身物成型、 焙烧后依次用含氟水溶液和镍-钨的 前身物水溶液浸渍， 每次浸渍后干燥和焙烧， 其中， 所述氧化铝 前身物为孔直径小于 80 埃孔的孔体积占总孔体积 95 % 以上的小 孔氧化铝的前身物和孔直径 60 - 600 埃孔的孔体积占总孔体积 70 %以上的大孔氧化铝的前身物的混合物， 混合物中小孔氧化铝前 身物与大孔氧化铝前身物的比例应使最终得到的催化剂载体中小 孔氧化铝与大孔氧化铝的重量比为 75: 25 ~ 50： 50. 虽然按照该 方法制备的催化剂的氧化铝载体中， 孔直径为 40 ~ 100 埃的孔体 积可以占总孔体积的 75 %以上， 该催化剂也是现有技术中加氢活 性最高的馏分油加氢精制催化剂之一， 但是， 由于该催化剂使用 了两种氧化铝， 其制备方法比较复杂。
此外， CN 1, 105， 053A 公开了一种适用于重质馏分油加氢精 制的催化剂， 该催化剂的组成为氧化镍 1 - 5 % , 氧化钨 15 - 38 重。 /。， 氟 1 ~ 9重％ , 其载体是一种用空气和水蒸汽在高温下处理 得到的改性氧化铝， 该改性氧化铝孔分布集中在 60 200 埃范围 以内， 由于采用了空气和水蒸汽在高温下处理的步骤， 该方法显 然存在制备工艺复杂、 能耗较高的缺点。
作为加氢催化剂的载体， 氧化铝的孔结构、 酸性及制备方法的 不同对催化剂性能有非常大的影响。 因此， 现有技术中有许多氧 化铝载体的制备方法， 以适应不同催化剂对载体性质的要求。 以 Y -氧化铝为例， 拟薄水铝石经焙烧后形成 γ -氧化铝， 后者是 常用的催化剂载体或基质。 γ -氧化铝作为催化剂的载体或基质 时， 其性质对整个催化剂的性能起着非常重要的作用。 一般来说， 要求拟薄水铝石的结晶度应较高。 三水氧化铝杂晶应较低， 最好 没有。 杂质离子的含量应较低， 氧化铝产品中酸根离子， 如疏酸 根离子的含量不大于 2重％ ,碱金属氧化物含量不大于 0. 15重％。 拟薄水铝石焙烧后形成的 Υ -氧化铝载体应具有较大的比表面， 较高的强度和适中的孔容， 同时， 应该有集中的孔分布。
现有技术中， 常用的一种制备拟薄水铝石和 Υ -氧化铝的方法 为偏铝酸钠 （或铝酸钠） -疏酸铝 （硝酸铝、 三氯化铝、 硝酸或 硫酸） 法。
US2, 980, 632 公开了一种氧化铝基催化剂的制备方法， 该方 法包括在 ρΗ 值 7 ~ 9. 5 的条件下， 从铝化合物的水溶液中沉淀出 水合氧化铝， 在较高的 ρΗ ( 10 ~ 11 ) 下老化浆液至少 0. 25 ~ 0. 5 小时。 所述水合氧化铝沉淀是将铝酸钠溶液和硫酸铝溶液进行中 和反应得到的， 所述较高的 pH值是通过減少硫酸铝溶液的用量来 实现的。 采用该方法制备拟薄水铝石时， 由于 pH值的调节是通过 减少硫酸铝溶液的用量来实现的， 因此， 铝酸钠的用量相对增多。 而在 pH 大于 10 以后， 铝酸钠易发生自水解反应， 生成三水氧化 铝， 一方面会覆盖在原沉淀的表面， 造成堵孔， 使生成的氧化铝 孔容较低， 另一方面， 使生成的氧化铝中生成过多的 η -氧化铝。 因此， 使用该方法制备的氧化铝不适合用作馏分油加氢精制催化 剂的载体。
US4, 371, 513 公开了一种适合形成球形颗粒氧化铝的制备方 法。 该方法包括在特殊的和控制反应物浓度、 反应温度、 时间和 pH 的条件下沉淀氧化铝， 并在高 pH 值下进行过滤。 具体地说， 该方法包括将一种氧化铝浓度 5~ 9 重％， 温度 130~ 160。F 足够 量的硫酸铝溶液加入到温度 140- 170°F的水中， 调节混合物的 pH 值为 2 5。 将一种氧化铝浓度 18- 22 重％ , 温度 130~ 160°F的 偏铝酸钠溶液和另一部分量的硫酸铝水溶液同时加入到上述混合 物中， 以沉淀氧化铝， 形成氧化铝浆液， 浆液的 pH值和温度保持 7~ 8和 140~ 180°F, 溶液加入速度保证中间体一水铝石和一水软 铝石的生成。 将浆液的 pH值调至 9.5 ~ 10.5, 过滤浆液， 滤饼经 洗涤后得到基本上纯的氢氧化铝。 用该方法制备的氧化铝的孔分 布在一个较宽的范围内 （孔直径 100 - 1000 埃的范围内） ， 孔分 布不集中。 不适合作为馏分油加氢精制催化剂的载体。
US4, 248, 852 公开了一种用作催化剂载体的氧化铝的制备方 法。 该方法包括在至少 建立一种 pH 值为 6~ 10 的氢氧化铝 晶种凝胶。 依次加入 （ a) —种铝化合物， 调节所述溶胶的 pH 值 小于 5 或大于 11， 使氢氧化铝晶体溶解， 和 （ b) —种中和试剂， 使 pH 回到 6- 10, 使水合氧化铝晶体成长。 然后再至少重复两次 加入所述铝化合物和所述中和试剂使水合氧化铝晶体继续成长。 干燥和焙烧所述水合氧化铝晶体。 用该方法制备的氧化铝具有较 大的比表面和控制在一定范围内 （ 0.5~ 2 毫升 /克） 的孔体积， 并且孔集中分布在孔直径 0~ 200或 100~ 500埃的范围内。 但是， 这种方法采用至少摆动 3次 pH的方法， 操作过于复杂。
GB2, 146， 633A 公开了一种用作催化剂载体的氧化铝的制备 方法， 该方法包括（ 1 ) 在 pH6.0~ 8.5和温度 50 ~ 65" 的条件下， 将一种硫酸铝溶液和一种铝酸钠溶液同时加入到去离子水中， 制 备出一种含无定形水合氧化铝的水浆液； （ 2) 在第一步制备的浆 液中加入足以中和第一步制备的浆液的铝酸钠溶液， 制备出氧化 铝含量至少为 7重％的第二种水浆液， 其中， 在步骤 （ 1) 和 （ 2) 中所用的铝酸钠的量相当于步骤（ 1 ) 中硫酸铝当量用量的 0.95~ 1.05; ( 3) 过滤出第二种水浆液中的无定形水合氧化铝， 并且依 次用氨水溶液、 硝酸溶液和氨水溶液洗涤滤饼， 使滤饼的最终 pH 为 7.5- 10.5; ( 4) 将 滤饼置于一个压滤装置上进行脱水使氧 化铝的含量增加到 28- 35重％ , 并且将脱水后的滤饼混捏至少 10 秒得到一种面团状物； （ 5) 将面团状物挤条， 干燥并焙烧挤出物。 该方法制备出的氧化铝作载体的催化剂的活性较低。 此外， 该方 法经过三次用氨水溶液和硝酸溶液洗涤滤饼的过程， 不仅操作复 杂， 而且产生的废水较多。
石油炼制， 11- 12， 50~ 57, 1978 公开了一种疏酸铝-偏铝酸 钠法制备 Y -氧化铝的方法，该方法包括将硫酸铝，偏铝酸钠及净水按 一定比例并流加入有搅拌器的中和罐中进行连续成胶，成胶的 pH 值 控制在 7.5~ 9.0,温度控制在 40- 70X:,停留时间 15分钟，成胶生成 的浆液在老化罐内收集，收集 30分钟后，维持一定温度，老化 30分钟， 过滤。 然后， 在滤饼中加入氧化铝投料量的 30 倍（重）的净水进行第 一次洗涤，洗涤初始加入一定量的碳酸钠调节浆液 pH值至 10.0，搅拌 洗涤 20分钟，过滤。再重复洗涤三次，但不再加入碳酸钠，在 110- 120 下干燥，在 550 下焙烧 4 小时，即得到 Y -氧化铝。 这种方法的关 键即是在第一次洗涤过程中加入碳酸钠调节 pH值至 10.0, 碳酸钠的 加入有两种作用： 一是可增加氧化铝的孔容， 二是可降低氧化铝中 硫酸根的含量。 但是， 从工业应用角度考虑， 这种洗涤过程加碳酸 钠的方法存在如下的缺陷： （ 1) 老化结束后要进行过滤，由于工业 滤机性能的限制，过滤过程中总是伴随着穿滤和跑漏现象，所以第一 次洗涤收集的滤饼中氧化铝的含量总是低于成胶过程中氧化铝的投 料量，而且由于工业生产中一般同时使用多台滤机，而滤机的过滤性 能存在差别，这就造成了第一次洗涤收集的氧化铝不仅少于成胶过程 的投料量，而且不同的批次收集的氧化铝量也存在差别。 由于碳酸钠 的用量是根据成胶过程中铝的投料量决定的，这就使碳酸钠的用量难 以确定， 工业上只能根据估计加以解决， 而这种估计有时出入很大。 碳酸钠的用量对氧化铝的孔容孔分布有非常重要的影响，因此上述的 碳酸钠的加入方式使得制备的氧化铝性能缺乏重复性，制备出的氧化 铝的性能非常不稳定， 由这种氧化铝制备的加氢催化剂的性能也非 常不稳定。 （ 2 ) 从连续化生产的角度考虑， 工业上滤机的选择以带 式滤机为好， 因为这种滤机可一次完成洗涤， 从而提高氧化铝的收 率和生产效率， 降低成本。 由于上述碳酸钠的加入是在洗涤过程中 完成的， 所以从老化到第一次洗涤必须经过一次过滤， 这就限制了 带式滤机的使用。
另一种常用的制备拟薄水铝石和 Y -氧化铝的方法为偏铝酸钠
-二氧化碳法。 由于该方法能结合铝厂工业实际情况， 可以以铝 土矿生产的偏铝酸钠溶液或铝酸钠溶液和二氧化碳废气为原料制 备氧化铝， 是一种廉价的方法， 因而， 该方法在工业上得到广泛 应用。
现有技术中， 偏铝酸钠溶液（或铝酸钠溶液）和二氧化碳的成胶 反应 （或称中和反应） 可以间歇或连续地进行。 在间歇式成胶反 应中， 是将 C02气体通入到大量的偏铝酸钠溶液或铝酸钠溶液中， 成胶反应的 pH值 （终点 pH值） 均控制在 9. 5， 最好 10以上。 在连续 成胶反应中， 偏铝酸钠溶液或铝酸钠溶液和二氧化碳各自以一定 的速度接触， 成胶反应的 pH值 （过程 pH值） 也控制在 9. 5, 最好 10 以上„ 在这种高 pH值下进行成胶反应， 可以得到结晶度较高的拟 薄水铝石 （γ -氧化铝的前身物） ， 但由于其晶粒形状为实心球状， 晶粒间堆积紧密， 因此经焙烧后生成的氧化铝的孔较小， 氧化铝 的孔直径介于 20- 60埃的孔占总孔容的 60%以上，这极大地限制了 其在馏分油加氢精制催化剂中的应用。
例如， US3，268，295公开了一种水合氧化铝的制备方法， 该水 合氧化铝含有每摩尔氧化铝 1.4- 1.6摩尔的结晶水， 平均晶粒大 小 20~ 40埃。 X光衍射谱图中 2Θ = 28. IX：峰的峰面积是一水软铝 石相应峰面积的 40- 90%。 该方法包括 （ a) 将钠含量小于约 200 克 Na2C03每升的铝酸钠与近似化学计量的二氧化碳反应， 制备基本 上不含结晶水合氧化铝的无定形氢氧化铝， 反应的条件为反应温 度 25~ 60 ， 反应时间 2~ 20分钟， pH值 10~ 11, 基本上由中和反 应而不是水解反应沉淀出氢氧化铝。 （ b) 从母液中分离出沉淀， 洗涤， 并且将沉淀与水重新打浆使沉淀分散， 使之处于无定形状 态。 （ c)在 100"C以下及 pH值 8~ 9下老化浆液中的沉淀 5~ 90分钟， 使无定形氢氧化铝转变成结晶形水合氧化铝。
EP0, 147， 167A2公开了一种连续中和铝酸盐溶液生产氧化铝凝 胶的方法， 该方法包括 （ a) 使具有一定总苛性度和一定氧化铝与 苛性度比值的铝酸钠溶液流入一个反应器； （b)将反应器中的溶液 保持一定的温度； （ c) 用一种中和试剂与该溶液接触， 使 pH值降 低到预定值， 所述中和试剂选自能溶于所述铝酸钠溶液的气体和 不溶于所述铝酸钠溶液的液体； （ d) 从反应器中连续移出生成的 氧化铝凝胶， 根据苛性度、 氧化铝与苛性度的比值， 反应温度， pH 及停留时间， 选择移出的速度使氧化铝凝胶形成特定形态。 在该 申请的第 7页指出， 根据所希望得到的产品不同， 中和反应的 PH值 可以从 8.5到 12, 例如， 当 pH为 8.5~ 10.2时可以得到丝钠铝石 ( dawsonite ) „ 当 pH约 12时可以得到三水铝石 ( gibbsite ) 。 而当 pH为 10.4 ~ 10.7, 将主要得到拟薄水铝石。
CN85, 100, 161A公开了一种利用氧化铝生产中的工业铝酸钠 溶液， 经碳酸化成胶生产拟薄水铝石的工艺方法。 该方法包括在 氧化铝浓度 70 130克 /升， 温度 70- ΙΟΟ 的工业铝酸钠溶液中加 入蒸馏水或去离子水， 稀释和冷却到氧化铝浓度 20- 60克 /升， 温 度 15- 45 X：。 然后将稀释冷却后的溶液过滤净化除去八1(0103残 渣， 再通入浓度为 30 - 45 %的二氧化碳气体进行快速碳酸化成胶。 碳酸化成胶分为间断和连续两种方式， 在采用间断碳酸化成胶时， 通 (：02气体速度 2 ~ 8克 C02/克 A1203■ 小时， 时间 10 ~ 30分钟。 采用 连续碳酸化成胶时， 通 ( 02气体速度 1 ~ 6 C02/克 A1203 · 小时， 碳 酸化过程为 30 - 90分钟。 成胶以后的浆液接着加热至 70 - 100 ， 温恒老化 1 - 6小时。 或者， 先直接进行液固分离后在洗涤过程中 加以老化。 分离得到的固体， 用温度 70 - ΙΟΟ Χ 的蒸馏水或去离子 水洗涤 1 - 4次， 洗涤液部分返回作稀释工业铝酸钠溶液用。 分离 出的母液和剩余洗涤液送回氧化铝生产流程。 最后， 将洗涤好的 湿物料按常规烘干和粉碎方式处理， 得到粉状拟薄水铝石。 根据 该申请所述成胶条件，其终点 pH值或过程 pH值也控制在 10. 5 ~ 12. 0 之间。
在用偏铝酸钠 （或铝酸钠） -二氧化碳法生产拟薄水铝石时， 现有技术中之所以把终点或过程 pH值控制在 10 ~ 12是因为在成胶 过程中， 当终点或过程 pH值小于 10, 特别是小于 9. 5时， 成胶过程 生 成 的 氢 氧化铝 和碳 酸 氢钠 发 生 作 用 生 成 丝钠 铝 石 ( NaAl (0H) 2C03 ) , 以偏铝酸钠 -二氧化碳法生产拟薄水铝石为 例， 成胶过程中存在如下反应：
2NaA102 + 3H20 + C02 ► 2A1 (OH) 3 + Na2C03
Na2C03 + H20 + C02 ► 2 NaHC03 +
Al (OH) 3 + NaHC03 ► NaAl (0H) 2( 03丄 + H20 因丝钠铝石不溶于水， 在洗涤过程中不能被除^, 因而在得到 的产品中钠含量太高， 这严重地影响了产品的性质。
US4, 500, 444公开了一种碱式碳酸铝胶体的方法， 该方法包括在 pH 为 6. 8±0. 2, 温度为 10 - 的水溶液中， 将偏铝酸钠与二氧化碳反应， 生成碱式碳酸铝胶体， 过滤， 从反应介质中分离出该胶体。 该胶体用酸 水解后可以生成拟薄水铝石。 用该方法制备的拟薄水铝石中， 疏酸根及 钠离子含量均显著降低。 但是， 该拟薄水铝石的结晶度、 孔容及孔径也 较低， 不适合用作馏分油加氢催化剂的载体。 同时， 由于酸的胶溶作用， 洗涤过程非常困难。 此外， 该方法由于要经过碱式碳酸铝的分解， 不仅 要消耗大量昂贵的有机酸， 增加生产成本， 而且会腐蚀设备。
发明目的
本发明的目的是提供一种新的， 具有更高催化活性的馏分油加 氢精制催化剂及其制备方法， 本发明的另一个目的是提供该催化剂 中所用的氧化铝载体及其制备方法。
发明详述
本发明提供的催化剂含有一种氧化铝载体和负载在该氧化铝载 体上的至少一种第 VIB 族金属和 /或氧化物及至少一种第 VIII 族金 属和 /或氧化物； 所述氧化铝载体的孔容不小于 0. 35 毫升 /克， 孔直 径为 40 - 100 埃孔的孔容占总孔容的 80 %以上， 它采用如下方法中 的一种或两种制备：
方法 1包括将偏铝酸钠或铝酸钠溶液与硫酸铝、 硝酸铝、 氯化铝、 硝酸和疏酸溶液中的一种或几种接触， 进行一次成胶反应， 成胶反 应可以以连续的方式进行， 老化得到的氢氧化铝， 将固体和液体分 离，洗涤，干燥并焙烧得到的固体产物。 其中， 所述一次成胶反应的 pH 值为 6 - 9. 5, 成胶反应的温度为 10 ~ 100 " , 成胶反应（一次成胶）生 成的浆液在二次成胶罐内收集，收集时间不少于 10分钟，收集完毕后， 将浆液切换到另一个二次成胶罐内继续收集。 在已收集完毕的二次 成胶罐内加入碱金属的碳酸盐，碱金属的碳酸氢盐与氨水的混合溶 液， 碳酸铵和碳酸氢铵中的一种或几种进行二次成胶， 二次成胶的 pH 值控制在 9. 0 ~ 10. 5。
其中， 所述偏铝酸钠或铝酸钠溶液的浓度以及疏酸铝、 硝酸 铝、 氯化铝、 硝酸和硫酸溶液的浓度可以是任意的、 可能存在的 浓度， 只要保证一次成胶反应的 pH值为 6 ~ 9. 5即可。 为保证高效 率地制备拟薄水铝石， 偏铝酸钠或铝酸钠溶液的浓度优选 30 - 300 克氧化铝 /升， 硫酸铝、 硝酸铝和氯化铝的浓度优选为 10 ~ 120克 氧化铝 /升， 硝酸和硗酸溶液的浓度优选为 5 ~ 15重％。
碳酸钠、 碳酸铵和碳酸氢铵等物质的加入可以以固体的形式 加入也可以 以水溶液的形式加入， 优选以水溶液的形式加入。 所述一次成胶反应的 pH值优选为 6~ 9。 一次成胶反应的温度 优选为 30~ 90t：。 收集时间优选为 10~ 90分钟。 二次成股的 pH值 优选为 9.5~ 10.5。
所述固液分离的方法可以采用常规的方法， 如可以采用过滤的 方法或离心分离的方法。
所述老化按常规的条件老化， 一般来说老化温度 5~ lOOC 优 选 30- 100 ， 更为优选 30 90 ， 老化时间大于 0.5小时， 优选 1 ~ 8小时。
所述洗涤按常规方法进行， 洗涤的目的是去除其中的杂质离 子， 如硫酸根离子、 钠离子等， 所述洗涤应使形成的氧化铝中碱 金属氧化物的含量不大于 0.15重％， 硫酸根离子的含量不大于 2重
% 。
制备氧化铝载体时， 在干燥之前还可以并优选有一个成型的步 骤。 成型的方法可以采用现有的各种方法， 如压片成型的方法、 成球成型的方法、 挤条成型的方法等， 优选采用挤条成型的方法。 在成型过程中可以加入现有的各种胶溶剂和 /或助挤剂。 所述胶溶 剂可以是各种无机酸或有机酸， 如盐酸， 硝酸、 柠檬酸、 醋酸等。 所述助挤剂可以是淀粉类物质、 纤维素类物质等。
所述干燥条件为常规的干燥条件， 干燥的温度可以是室温至拟 薄水铝石转晶温度以下， 优选 100- 200 。
所述焙烧条件为常规的焙烧条件， 如焙烧温度 500- 900C 优 选 550~ 850Χ , 焙烧时间 2~ 8小时， 优选 3~ 6小时。
方法 2包括将偏铝酸钠或铝酸钠溶液与含二氧化碳的气体接 触， 以间歇或连续的方式成胶， 老化得到的氢氧化铝， 将固体和 液体分离，洗涤，干燥并焙烧得到的固体产物。 其中， 所述成胶的 终点 ΡΗ值或过程 pH值控制在 6~ 9.5的范围内， 成胶反应的时间或 停留时间少于 40分钟， 成胶反应的温度 10- 100" ， 成胶反应结束 后迅速加入碱性物质， 使浆液的 pH值上升至 9.5以上或迅速进行固 液分离并洗涂。 其中， 所述偏铝酸钠或铝酸钠溶液的浓度可以是任意的、 可能 存在的浓度， 为保证高效率地制备拟薄水铝石， 偏铝酸钠或铝酸 钠溶液的浓度优选为 5 ~ 200克氧化铝 /升， 更优选为 5 ~ 120克氧化 铝 /升。
所述含二氧化碳的气体可以是纯的二氧化碳气体， 也可以是由 二氧化碳和不影响反应的惰性气体组成的混合气体， 如空气、 氮 气、 氦气、 氩气等气体中的一种或几种与二氧化碳的混合气。 含 二氧化碳的气体中二氧化碳的含量可以在很大范围内变动， 一般 情况下， 二氧化碳含量不小于 5体积％ , 优选不小于 20体积％。
所述成胶反应可以是间歇式的。 采用这种方式时， 首先将偏铝 酸钠或铝酸钠溶液置于一成胶罐中， 从罐的底部通入含二氧化碳 的气体， 反应温度控制在 10 - 100 Ό , 优选 10 80 ：, 终点 PH值控 制在 6 - 9. 5 , 优选 6. 5 9. 3。 通过调节偏铝酸钠或铝酸钠溶液的 浓度、 用量及含二氧化碳气体的浓度及流量， 使成胶反应的时间 不超过 40分钟， 优选不超过 30分钟。 成胶反应结束后， 迅速加入 碱性物质， 使浆液的 PH值迅速上升到 9. 5以上， 优选 9. 5 - 11. 5之 间， 或迅速进行固液分离并洗涤。 然后在常规条件下老化、 过滤、 洗涤并干燥， 得到拟薄水铝石， 焙烧后形成氧化铝载体。
所述成胶反应也可以是连续的。 当采用这种成胶方式时， 首先 在一成胶罐中预先加入去离子水， 同时从罐的底部通入含二氧化 碳的气体并从罐的顶部通入偏铝酸钠或铝酸钠溶液， 使偏铝酸钠 或铝酸钠溶液与含二氧化碳的气体逆流接触， 控制成胶温度 10 - 100 , 优选 10 ~ 80 X ， 控制偏铝酸钠或铝酸钠溶液的浓度和流速 及含二氧化碳气体的浓度和流速使成胶过程 pH值在 6 ~ 9. 5 , 优选 6. 5 - 9. 3之间， 并且使停留时间不超过 40分钟， 优选不超过 30分 钟。 成胶过程生成的浆液连续或间断地收集到一个老化罐中， 连 续或间断地加入碱性物质使浆液 pH值上升至 9. 5以上， 优选 9. 5 ~ 11. 5之间。 收集一段时间后， 将成胶反应生成的浆液切换到另一 个老化罐， 并对第一个老化罐内 pH值大于 9. 5的浆液进行老化， 过 滤、 洗涤并干燥， 得到拟薄水铝石， 焙烧后得到氧化铝载体。 所述碱性物质选自无机碱、 有机碱和它们水溶液中的一种或几 种。 其中所述无机碱优选碱金属的氢氧化物、 偏铝酸盐、 碳酸盐、 碳酸氢盐、 碳酸铵、 氨水及它们的水溶液中的一种或几种。 所述 有机碱优选水溶性胺类、 脲、 吡啶及它们的水溶液中的一种或几 种， 优选溶于水的脂肪族胺类、 烃基氢氧化铵、 尿素、 吡啶及它 们的水溶液中的一种或几种， 特别是甲胺、 乙胺、 丙胺、 丙二胺、 丁胺的各种异构体、 戊胺的各种异构体、 四乙基氢氧化铵、 尿素、 吡嚏及它们的水溶液中的一种或几种。
所述固液分离的方法可以采用过滤的方法或离心分离的方法。 迅 速进行固液分离以后的洗涤是为了去除其中能生成丝钠铝石的反应 物碳酸氢钠， 一般用不小于 10倍固体产物重的去离子水洗涤至少一 次。
所述老化按常规的条件老化， 一般来说老化温度 5 ~ lOO C 优 选 30 ~ 100 "C， 更为优选 50 100 , 老化时间大于 0. 5小时， 优选 1 - 8小时。 采用加入碱性物质调节 pH值的方法时， 老化的介质可 以是母液或去离子水。 采用迅速进行固液分离的方法时， 老化的 介质一般是去离子水。
所述老化后的洗涤按常规方法进行， 洗涤的目的是去除其中的 杂质离子， 使其中碱金属氧化物的含量小于 0. 15重％。
所述干燥条件为常规的干燥条件， 干燥的温度可以是室温至拟 薄水铝石转晶温度以下， 优选 100 ~ 200 X 。
制备氧化铝载体时， 在干燥之前同样可以并优选有一个如前所 述的成型步骤。
所述焙烧条件为常规的焙烧条件， 如焙烧温度 500 - 900 C， 优 选 550 ~ 850 " ， 焙烧时间 2 ~ 8小时， 优选 3 6小时。
按照本发明提供的催化剂， 所述第 VIB族金属和 /或氧化物指铬、 钼、 钨金属和它们的氧化物中的一种或几种， 优选为钼、 钨金属和 它们的氧化物中的一种或几种， 更优选为钨和 /或其氧化物。 以氧化 物计， 所述第 VIB族金属的含量为 12 ~ 35 重％。
按照本发明提供的催化剂， 所述第 VIII 族金属和 /或氧化物指 铁、 钴、 镍、 钌、 铑、 钯、 锇、 铱、 铂金属和它们的氧化物中的一 种或几种， 优选为钴、 镍金属和它们的氧化物中的一种或几种， 更 优选为镍和 /或其氧化物。 以催化剂总量为基准并以氧化物计， 所述 第 VI II族金属的含量为 1 - 5 重％。
以催化剂总量为基准，本发明提供的催化剂还可以并优选含有 1 ~ 9 重％的氟。
本发明提供的催化剂的制备方法包括用含第 VIB族和第 VIII 族 金属的水溶液浸渍催化剂载体， 浸渍后干燥并焙烧， 其中所述催化 剂载体为方法 1和 /或方法 2制备的氧化铝载体。
所述含第 VIB族和第 VI I I 族金属的水溶液指含第 VIB族和第 VI I I 族金属化合物的水溶液， 其中优选含钼和 /或钨及镍和 /或钴 化合物的水溶液， 如含偏钨酸铵、 钨酸铵、 乙基偏钨酸铵、 钼酸 铵中的一种或几种及含偏钨酸镍、 硝酸镍、 醋酸镍、 硝酸钴、 醋 酸钴中的一种或几种的混合水溶液。 更为优选含钨和镍化合物的 水溶液， 如含偏钨酸铵、 钨酸铵、 乙基偏钨酸铵中的一种或几种 和偏钨酸镍、 硝酸镍、 醋酸镍中的一种或几种的混合水溶液。
其中， 在用含第 VIB族和第 VI II 族金属的水溶液浸渍催化剂载 体之前， 还可以并优选包括用含氟水溶液浸渍催化剂载体， 干燥并 焙烧的步骤。 所述含氟水溶液指含氟的无机化合物水溶液， 如氟化 铵和 /或氟化氢的水溶液。
用含第 VIB族和第 VI II 族金属的水溶液浸渍催化剂载体或用 含氟水溶液浸溃催化剂载体之后的干燥均为常规的干燥条件， 干 燥温度可以从室温至 300 , 优选 100 ~ 200 。
用含第 VIB族和第 VI II 族金属的水溶液浸渍催化剂载体或用 含氟水溶液浸渍催化剂载体之后焙烧温度均为 400 - 600 TC , 焙烧 时间为 1 - 8 小时， 优选 2 5小时。
按本发明提供的方法 1制备氧化铝载体时， 碱金属的碳酸盐、 碱金属的碳酸氢盐和氨水的混合溶液、 碳酸氢铵及碳酸铵的加入 是在老化和过滤前完成的， 可以根据氧化铝的投料量， 准确地加 入碱金属的碳酸盐、 碱金属的碳酸氢盐和氨水的混合溶液、 碳酸 氢铵及碳酸铵， 这样就克服了现有技术在洗涤过程中加入碳酸钠 的方法存在的碳酸钠计量难于控制的缺点。 采用本发明提供的方 法 1 制备的氧化铝的前身物拟薄水铝石呈纤维状， 制备成的氧化 铝载体不仅孔容为 0. 45 - 0. 75 毫升 /克， 孔直径介于 40 ~ 100埃的 孔的孔容占总孔容 80 % 以上， 而且重复性好， 得到的氧化铝载体 的性质非常均匀， 质量稳定可靠。 该氧化铝特别适合用作馏分油 加氢精制催化剂的载体。
本发明的发明人发现， 在偏铝酸钠或铝酸钠与二氧化碳进行成 胶反应的过程中， 当终点或过程 pH值小于 9. 5 时， 虽可伴随碳酸 钠与氢氧化铝作用生成丝钠铝石的反应， 但是， 该反应需要有足 够的时间才能完成， 这个时间一般需要 40 分钟或更长一点的时 间， 当成胶 pH值小于 9. 5 时， 只要保证低 pH值的时间不超过 40 分钟， 即可得到基本上无丝钠铝石的拟薄水铝石。 然而， 众所周 知， 生成的氢氧化铝需要老化， 老化的时间一般大于 0. 5 小时， 加上成胶的时间， 肯定会超过 40分钟。 根据上述情况， 本发明人 巧妙地发明出如方法 2 所述的方法。 方法 2 克服了现有技术偏铝 酸钠或铝酸钠 -二氧化碳法制备的拟薄水铝石晶粒呈实心球状， 晶粒间堆积紧密， 焙烧后形成的氧化铝孔容较小， 孔径较小的缺 点。 方法 2 制备的拟薄水铝石呈纤维状， 焙烧后形成的氧化铝载 体的孔容为 0. 45 - 0. 75 毫升 /克， 孔直径介于 40 100 埃的孔的 孔容占总孔容的 80 % 以上， 这种性盾的氧化铝载体特别适合用作 馏分油加氢精制催化剂载体。
由于采用了上述特殊方法制备的具有特殊性质的氧化铝载体， 本发明提供的催化剂具有比现有技术更高的催化活性。 例如， 其脱 疏、 脱氮及芳烃饱和加氢活性均高于 CN 85104438 B中所披露的催化 剂， 而且当本发明提供的催化剂用于高硫劣盾馏分油加氢精制时， 仍具有较高的催化活性。 又例如， 本发明提供的催化剂在堆比 （装 填密度） 较低 （ 0. 78 - 0. 88克 /毫升） 的情况下， 加氢脱疏、 脱氮及 芳烃饱和性能仍高于 CN 85104438 B披露的催化剂的相应活性（其堆 比〉 1. 0克 /亳升）， 即本发明提供的催化剂在更大的空速下仍然具有 更高的加氢活性。
此外， 本发明提供的催化剂还保持了 CN 85104438 B 披露的催 化剂金属含量较低的优点。 不仅如此， 利用本发明所述的方法 1 和 方法 2制备的氧化铝载体的成本非常低， 其成本只有 CN 85104438 B 所用载体成本的 15 50 %。 因此， 本发明提供的催化剂的成本也大 幅度的降低， 本发明提供的催化剂是一种活性高而且低成本的催化 剂， 具有很大的工业应用价值。
本发明提供的氧化铝载体除特别适合用作馏分油加氢精制催化剂 载体外还特別适合用作馏分油加氢裂化催化剂的载体或基质。
本发明提供的催化剂特别适用于馏程为 80 - 550X 的石油馏分油 的加氢精制， 本发明提供的催化剂和加氢裂化催化剂配合使用则可 用于重质馏分油的加氢改质， 特别是中压加氢改质过程。
本发明提供的催化剂用于馏分油加氢精制时可使用常规的加氢精 制工艺条件， 如反应温度 200 ~ 500 ， 优选 300 - 反应压力
2 ~ 24兆帕， 优选 3 ~ 15兆帕， 液时空速 0. 1 - 30小时 1优选 0. 2 - 10小时 氢油体积比 50 - 5000, 优选 200 - 1000。
附图说明
图 1是本发明提供的氧化铝载体的前身物拟薄水铝石的透射电镜 照片。
图 2是现有技术拟薄水铝石的透射电镜照片。
图 3是本发明提供的氧化铝载体的前身物拟薄水铝石的透射电镜 照片。
图 4是现有技术拟薄水铝石的透射电镜照片。
实施例
下面的实施例将对本发明做进一步说明， 但并不以任何形式限制 本发明。
实例 1
本实例说明本发明提供的氧化铝载体及其制备。
将浓度为 250克氧化铝 /升的 NaA102溶液和浓度为 100克氧化铝 / 升的 A12 (S04) 3溶液以并流的方式同时加入到一个 2升的成胶罐（一 次成胶罐）中，罐中预先放入 1. 5升水， NaA102溶液的流量为 1. 1升 / 小时，调节 Al2 (S04) 3溶液的流量，使成胶 pH值为 8. 0,成胶过程的温 度为 50 ，成胶生成的浆液在一个二次成胶罐（二次罐）内收集，收 集 20分钟后，将浆液切换到另一个二次罐内收集。 已收集完毕的二 次罐内加入碳酸钠调节 pH值至 10. 0,然后老化 50分钟，过滤，用 30倍 去离子水洗涤 4次后，将滤饼于 烘干，得拟薄水铝石， 图 1给出 了拟薄水铝石放大 5万倍的透射电镜照片， 从其透射电镜照片看， 拟薄水铝石呈纤维状。 将得到的拟薄水铝石磨碎， 按常规的挤条 条件， 加入水、 胶溶剂硝酸和助挤剂淀粉挤成直径为 1. 4毫米的三 叶型条， 将成型物于 110 - 120 X 下烘干， 于 550 焙烧 5小时， 得 氧化铝载体 其性质如表 1所示。
实例 2
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中 &八102溶液的浓度变为 50克氧化铝 /升，流量变为 5. 3 升 /小时， A12 (S04) 3溶液浓度变为 30克氧化铝 /升，并调节其流量使 成胶 PH值为 8. 0，其它条件不变， 得到的氧化铝载体 A2，其性盾如表 1所示。
实例 3
本实例说明本发明提供的氧化铝载体及其制备。
调节实例 1中 A12 (S04) 3溶液流量， 使成胶 pH值变为 6. 5，其它条 件不变，得氧化铝载体 A3，其性质如表 1所示。
实例 4
本实例说明本发明提供的氧化铝载体及其制备。
调节实例 1中 A12 (S04) 3溶液流量， 使成胶 pH值变为 9. 0，其它条 件不变，得氧化铝载体 A4，其性质如表 1所示。
实例 5
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中成胶温度变为 75 ，并调节 A12 (S04) 3溶液流量， 使成 胶 pH值维持 8. 0，其它条件不变，得氧化铝载体 A5，其性质如表 1所 示。 实例 6
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中浆液的收集时间变为 80分钟，其它条件不变，得氧化 铝载体 A6，其性质如表 1所示。
表 1
Figure imgf000019_0001
实例 7
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中 A12 (S04) 3溶液变为氧化铝含量相同的 A1 (N03) 3溶液， 其它条件不变，得氧化铝载体八7，其性质如表 2所示。
实例 8
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中 A12 (S04) 3溶液变为氧化铝含量相同的 A1C13溶液，其 它条件不变，得氧化铝载体 A8，其性质如表 2所示。
实例 9
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中 A12 (S04) 3溶液变为浓度为 5重％的硫酸，其它条件不 变，得氧化铝载体 A9，其性质如表 2所示。
实例 10
本实例说明本发明提供的氧化铝载体及其制备。 将实例 1中 A12 (S04) 3溶液变为浓度为 7重％的硝酸，其它条件不 变，得氧化铝载体 A1()，其性质如表 2所示。
实例 11
本实例说明本发明提供的氧化铝载体及其制备。
将实例 1中碳酸钠换成碳酸氢铵和氨水的混合溶液，其中碳酸氢 铵的浓度为 50克 /升，氨水浓度为 5重％，调整后的 PH值为 9. 5，其它 条件不变，得氧化铝栽体 A 其性质如表 2所示。
实例 12
本实例说明本发明提供的氧化铝栽体及其制备。
将实例 1中碳酸钠换成浓度为 50克 /升的碳酸铵溶液，并调整浆 液 pH值为 9. 5，其它条件不变，得氧化铝载体 A12，其性盾如表 2所 示。
对比例 1
参比氧化铝载体的制备。
按 GB2, 146, 633A公开的方法制备氧化铝载体。 按实例 1 的 方法制备氧化铝载体， 不同的是在收集 20分钟的浆液中加入 0. 37 升实例 1 所述的偏铝酸钠溶液， 过滤、 并且依次用氨水溶液、 硝 酸溶液和氨水溶液洗涤滤饼， 使滤饼的最终 pH 为 10。 将滤饼挤 压脱水使氧化铝的含量增加到 30 重％ , 并且将脱水后的滤饼混 捏， 按实例 1 所述的方法挤条成型、 干燥并焙烧， 得到的参比氧 化铝载体 AB^ 的物化性质列于表 3 中。 其中， 图 2 给出了滤 饼混捏烘干后得到的拟薄水铝石的放大 5 万倍的透射电镜照片， 从其透射电镜照片看， 该拟薄水铝石呈粒状。
对比例 2
参比氧化铝载体的制备。
按 US2, 980， 632 公开的方法制备氧化铝载体。 按实例 1 的方 法制备氧化铝载体， 不同的只是在收集 20 分钟浆液后减少硫酸铝的 流量， 使浆液的 pH值上升至 10. 0, 得参比氧化铝载体 AB2。 AB2的 物化性质列于表 3中。 表 2
Figure imgf000021_0001
表 3
Figure imgf000021_0002
实例 13
本实例说明本发明提供的氧化铝载体及其制备。
取 20升浓度为 10克氧化铝 /升的偏铝酸钠溶液， 置于一个 25升 的成胶罐中， 初始温度 15C 从成胶罐的底部通入二氧化碳含量 30 体％的二氧化碳和空气的混合气， 混合气的流量为 22米 V小时， 反应 3分钟， 11值降到6.5， 此时反应温度为 22Χ， 迅速加入浓度 为 200克 /升的碱性物质碳酸钠溶液， 使浆液 ρΗ值在 4分钟内升至 9.8。 升温至 32 :， 恒温老化 4小时。 过滤， 用 20倍 90Χ去离子水 洗涤 2次， 120 烘干， 得到拟薄水铝石。 图 3给出了拟薄水铝石放 大 5万倍的透射电镜照片， 从其透射电镜照片看， 拟薄水铝石呈纤 维状。 按实例 1所述的方法成型、 干燥和焙烧， 得氧化铝载体 A13„ 表 4给出了 A13的物化性质。
实例 14
本实例说明本发明提供的氧化铝载体及其制备。
按实例 13的方法制备氧化铝载体， 不同的是用碱性物质氢氧化 钠代替碱性物质碳酸钠溶液， 使浆液 pH值在 1分钟之内上升至 9. 8, 得到氧化铝载体 A14。 表 4给出了 A14的物化性质。
实例 15
本实例说明本发明提供的氧化铝载体及其制备。
按实例 13的方法制备氧化铝载体， 不同的是用碱性物质氢氧化 钾代替碱性物质碳酸钠溶液， 使浆液 pH值在 3分钟上升至 9. 8， 得 氧化铝载体 A15。 表 4给出了 A15的物化性质。
实例 16
本实例说明本发明提供的氧化铝载体及其制备。
按实例 13的方法制备氧化铝载体， 不同的是用浓度 2重％的氨 水代替碱性物质碳酸钠溶液， 使浆液 pH在 7分钟内上升至到 9. 8， 得氧化铝载体 A16。 表 4给出了 A16的物化性质。
实例 17
本实例说明本发明提供的氧化铝载体及其制备。
按实例 13的方法制备氧化铝载体， 不同的是用碱性物质碳酸铵 代替碱性物盾碳酸钠溶液， 在 9分钟之内使浆液的 pH值上升到 9. 5, 得氧化铝载体 A17。 表 4给出了 A17的物化性质。
Figure imgf000023_0001
实例 18
本实例说明本发明提供的氧化铝载体及其制备。
将 4升浓度为 60克氧化铝 /升的偏铝酸钠溶液置于一个 6升的成 胶罐中， 初始温度 60 ， 从罐底部通入二氧化碳含量为 90体％的 二氧化碳和空气的混合气， 混合气的流量为 5. 7米 V小时， 反应 15 分钟， pH值降到 8. 8, 此时反应温度为 73 ， 停止成胶反应， 迅速 加入碳酸钠， 使浆液 pH值在 9分钟内升至 11. 0。 将温度升至 90 X , 老化 45分钟， 过滤， 用 20倍 的去离子水洗涤四次， HO 烘干， 按实例 1的方法挤条成型、 干燥并焙烧， 得氧化铝载体 A18。 表 5给 出了 A18的物化性质。
实例 19
本实例说明本发明提供的氧化铝载体及其制备。
按实例 18的方法制备氧化铝栽体， 不同的只是偏铝酸钠溶液的 浓度为 80克氧化铝 /升， 反应 20分钟后 pH值降至 9. 3时即停止成胶 反应， 得氧化铝载体 A19。 表 5给出了 A19的物化性质。
实例 20
本实例说明本发明提供的氧化铝载体及其制备。
按实例 18的方法制备氧化铝栽体， 不同的是偏铝酸钠溶液的浓 度为 40克氧化铝 /升， 反应初始温度 30 ， 反应 12分钟后 pH值降至 7. 8, 此时的反应温度为 45 X 。 碳酸钠的加入量使浆液 PH值在 7分 钟内升至 10. 20。 老化温度 80 " , 老化时间 30分钟， 得氧化铝载体 A2。。 表 5给出了 A2。的物化性质„
实例 21
本实例说明本发明提供的氧化铝载体及其制备。
按实例 18的方法制备氧化铝， 不同的是老化温度为 33 , 洗涤 用去离子水温度为 33 C 得氧化铝载体 A21。 表 5给出了 A21的物化 性 。
Figure imgf000024_0001
实例 22
本实例说明本发明提供的氧化铝载体及其制备。
在一个 400毫升成胶罐中预先加入 150毫升去离子水， 初始去 离子水温度为 30 C 在罐的底部通入二氧化碳含量 35体％的二氧 化碳和空气的混合气， 混合气流量为 0. 7米 V小时， 同时从罐的上 方通入浓度为 100克氧化铝 /升的偏铝酸钠溶液， 使偏铝酸钠溶液 与混合气逆流接触， 偏铝酸钠溶液的流量为 10毫升 /分钟， 成胶过 程 pH值为 8. 2 ± 0. 2， 反应温度维持在 40 ± 2 ， 15分钟后开启成胶 罐底部的阀门， 使生成的浆液流入一个预先盛有 200毫升温度为 35 的去离子水的老化罐内， 流出的速度使成胶罐内的液面既不上 升也不下降。 并且以 25毫升 /分钟的速度加入浓度为 50克 /升的碱 性物质碳酸钠溶液， 调整老化罐内浆液的 pH值保持在 10. 0 ± 0. 1， 温度维持在 40 ± 2 。 收集 200分钟后， 将成胶生成的浆液切换到 另一个同样的老化罐中， 同时将碱性物质碳酸钠溶液切换到该老 化罐中。 将第一个老化罐中的浆液在 40 ± 2 的温度下老化 4小时， 过滤， 用 20倍 90 Χ 的去离子水洗涤 2次， 120 烘干， 按实例 1所述 方法挤条成型、 干燥，在 600 Χ 焙烧 4小时，得氧化铝载体 Α22。 表 6给 出了 Α22的物化性质。
实例 23
本实例说明本发明提供的氧化铝载体及其制备。
按实例 22的方法制备氧化铝载体， 不同的是控制成胶反应的温 度为 65 ± 2 Χ ， 收集成胶反应生成的浆液时老化罐内的温度为 65 土 老化温度 75 ± 2 , 得氧化铝载体 A23。 表 6给出了 A23的物化 性质。
实例 24
本实例说明本发明提供的氧化铝载体及其制备。
按实例 22的方法制备氧化铝载体， 不同的是成胶反应用偏铝酸 钠溶液的浓度为 50克氧化铝 /升， 流量为 24毫升 /分钟， 混合气中 二氧化碳浓度为 75体％ , 流量为 0. 33米 3/小时， 得氧化铝载体 A24。 表 6给出了 A24的物化性质。
实例 25
本实例说明本发明提供的氧化铝载体及其制备。
按实例 22的方法制备氧化铝， 不同的是混合气的流量为 0. 85 米 3/小时， 过程 pH值为 7. 0 ± 0. 2 , 作为碱性物质的碳酸钠溶液的 流量为 30毫升 /分钟， 得氧化铝载体 A25。 表 6给出了 A25的物化性质。
实例 26
本实例说明本发明提供的氧化铝载体及其制备。
按实例 13的方法制备氧化铝， 不同的是成胶反应结束后不加碱 性物质， 而是迅速过滤， 滤饼用 20倍 90 X 的去离子水洗涤两次， 将洗涤后的滤饼与 10倍的去离子水混合， 在 老化 4小时， 过滤„ 其他条件同实例 13, 得氧化铝 A26。 表 6给出了 A26的物化性质。 实例编号 22 23 24 25 26 氧化铝编号 A22 A23 A24 A25 八26 比表面， 米 2/克 254 267 259 272 258 孔容， 毫升 /克 0. 60 0. 62 0. 71 0. 64 0. 65 孔直径分布， ％
20 ~ 40埃 3 CO. 8 0. 2 2. 5 2. 4 3. 0
40 ~ 100埃 t 92. 7 87. 5
100 ~ 600埃 8. 0 7. 2 3. 7 10. 1 8. 0 对比例 3
参比氧化铝载体的制备。
将 4升浓度为 60克氧化铝 /升的偏铝酸钠溶液置于 6升成胶罐 中， 从罐底部通入二氧化碳含量 35体％的二 00氧化碳与空气的混合 气， 混合气的流量为 3. 3米 V小时， 反应初始温度 30 Χ , 反应 20分 钟后 ρΗ降至 10. 50, 此时反应温度为 停止成胶反应， 将温度 升至 95 "C , 老化 4小时， 过滤， 用 20倍 的去离子洗涤 4次， 120 X 烘干， 得拟薄水铝石， 图 4给出了该拟薄水铝石放大 5万倍的电 镜照片， 从电镜照片上看， 该拟薄水铝石呈堆积紧密的实心0 0球状。 按实例 1所述方法挤条成型， 550 焙烧 5小时得参比氧化铝载 o体 ΑΒ3。 表 7给出了 ΑΒ3的物化性质。
对比例 4
参比氧化铝载体的制备。
将对比例 3的成胶反应终点 ρΗ值降至 8. 5 , 反应时间为 55分钟， 其它条件不变， 干燥后的产物经 X射线衍射分析为丝钠铝石 ( NaAl (0H) 2C03 ) , 按实例 1所述方法成型， 干燥并焙烧后得到参 比氧化铝载体 AB4, 其物化性质列于表 7中。
对比例 5
参比氧化铝载体的制备。 实例 22中不加入碱性物质偏铝酸钠调整浆液的 pH值， 其它条件 不变， 干燥后的产物经 X光衍射分析为丝钠铝石， 按实例 1所述方 法成型， 干燥并焙烧后得到参比氧化铝载体 AB5， 其物化性质列于 表 7中。
对比例 6
参比氧化铝载体的制备。
按实例 22的方法制备氧化铝载体， 不同的是混合气的流量为 0. 45米 3/小时， 过程 pH值控制在 10. 5 ± 0. 1 , 不加入碱性物质碳酸 钠溶液， 得氧化铝载体 AB6。 AB6的物化性质列于表 7中。
表 7
Figure imgf000027_0001
实例 27 52
下面的实例说明本发明提供的馏分油加氢精制催化剂及其制 备。
分别称取实例 1 10 制备的氧化铝 A - Ai。及实例 13 26 制 备的氧化铝 A13 ~ A26各 200克， 分别用浓度为 4. 53 重％的氟化铵 溶液 200毫升浸渍 1 小时。 取实例 11制备的氧化铝 λη 200克，用 浓度为 3. 47 重％的氟化铵溶液 200 毫升浸渍 1 小时。 取实例 12 制备的氧化铝 Α12 200克，用浓度为 10. 6重％的氟化铵溶液 200毫 升浸渍 1 小时。 然后，将所有浸氟后的氧化铝于 120 烘干， 500 焙烧 4小时。 取浸氟焙烧后的氧化铝 Α7，用含氧化钨 35. 0克 /毫 升和氧化镍 2. 78 克 /毫升的偏钨酸铵和硝酸镍的混合溶液 180 毫 升浸渍 2 小时。 取浸氟焙烧后的氧化铝 A8，用含氧化钨 35.0克 / 毫升和氧化镍 5.55 克 /毫升的偏钨酸铵和硝酸镍的混合溶液 180 毫升浸渍 2小时。 取浸氟焙烧后的氧化铝 A9，用含氧化钨 22.2克 / 毫升和氧化镍 3.61 克 /毫升的偏钨酸铵和硝酸镍的混合溶液 180 毫升浸渍 2小时。 取浸氟焙烧后的氧化铝 A1()，用含氧化钨 43.0克 /毫升和氧化镍 3.61 克 /毫升的偏钨酸铵和硝酸镍的混合溶液 180 毫升浸渍 2 小时。 其余浸氟焙烧的氧化铝均分别用含氧化钨 31.6 克 /毫升和氧化镍 3.20 克 /毫升的偏钨酸铵和硝酸镍的混合溶液 180毫升浸渍 2小时， 然后所有浸渍钨和镍后的样品于 烘干， 再于 500X焙烧 4 小时， 得催化剂 （^~ (26。 催化剂中氧化钨， 氧 化镍和氟的含量分别列于表 8- 11 中。 其中， 氧化钨和氧化镍含 量测定方法参见 《石油化工分析方法》 （ RIPP 试验法） ， P360- 361, 科学出版社 （ 1990) 。 氟的测定方法参见同书的 P185- 187 页。
对比例 7~ 8
下面的对比例说明参比催化剂的制备。
按实例 27 所述的方法制备催化剂， 不同的是所用氧化铝载体分 别为对比例 1和 2制备的氧化铝栽体八81和 AB2, 得到的参比催化剂 编号为 ^和 ^， 81和 的氧化钨、 氧化镍和氟的含量列于表 12中。
对比例 9~ 10
下面的对比例说明参比催化剂的制备。
按实例 27 所述的方法制备催化剂， 不同的是所用氧化铝载体分 别为对比例 3和 6制备的氧化铝载体 83和 AB6, 得到的参比催化剂 编号为 ^和 ^， 83和 的氧化钨、 氧化镍和氟的含量列于表 12中。
对比例 11
下面的对比例说明参比催化剂的制备。
按实例 27所述方法制备催化剂， 不同的是所用氧化铝载体为 CN 85104438B 中实例 2 所用的氧化铝载体， 得到的参比催化剂编号为 B5。 B5的氧化钨、 氧化镍和氟的含量列于表 12 中。 表 8
实例编号 27 28 29 30 31 32 所用载体编号 A2 A3 A4 A5 A6 催化剂 c2 c3 c4 c5 c6 氧化钨含量， 重 21. 3
%
氧化镍含量， 重 2. 3
%
氟含量， 重％ 3. 0
比表面， 米 2/克 164 159 169 152 177 183 孔容， 毫升 /克 0. 50 0. 45 d 0. 44 0. 48 0. 52
O L
堆比， 克 /毫升 0. 82 0， 84 0. 790 0 0. 84 0. 83 0. 81 表 9
实例编号 33 34 35 36 37 38 所用载体编号 A7 A8 A9 Aio Au A12 催化剂 c7 c8 c9 Cio Cn C 2 氧化钨含量， 重％ 23. 6 23. 6 15. 0 30. 0 23. 6 23. 6 氧化镍含量， 重％ 2. 0 4. 0 2. 6 2. 6 2. 6 2. 6 氟含量， 重％ 4. 5 4. 5 4. 5 4. 5 2. 3 7. 0 比表面， 米 2/克 164 168 165 160 159 158 孔容， 毫升 /克 0. 54 0. 42 0. 52 0. 41 0. 57
Figure imgf000029_0001
堆比， 克 /毫升 0. 80 0. 85 0. 81 0. 85 0. 79 0. 79
表 10
实例编号 39 40 41 42 43 44 45 所用载体编号 Ai3 A14 A15 Ai6 A17 Ai8 ^19 催化剂 ◦13 c14 c15 Ci6 C17 Ci8 ^19 氧化钨含量， 重 21. 3
%
氧化镍含量， 重 2. 3
%
氟含量， 重％ 3. 0
比表面， 米 V克 162 165 169 165 160 163 170 孔容， 毫升 /克 0. 46 0. 40 0. 42 0. 47 0. 51 0. 59 0. 52 堆比， 克 /毫升 0. 84 0. 86 0. 85 0. 84 0. 82 0. 78 0. 82 表 11
实例编号 46 47 48 49 50 51 52 所用载体编号 A20 ^21 A22 A23 A24 A25 A26 催化剂 C20 ^21 C22 C23 C25 ◦26 氧化钨含量， 重％ 21. 3
氧化镍含量， 重％ 2. 3
氟含量， 重％ 3. 0
比表面， 米 2/克 185 173 158 171 159 165 157 孔容， 毫升 /克 0. 60 0. 55 0. 48 0. 50 0. 57 0. 51 0. 52 堆比， 克 /毫升 0. 78 0. 80 0. 84 0. 82 0. 80 0. 81 0. 81 表 12
Figure imgf000031_0001
实例 53 78
下面的实例说明本发明提供的催化剂的加氢脱硫活性。
将得到的条形催化剂 （^- (26分别截成长度为 2-3 毫米的条， 在 100亳升固定床加氢反应装置上用表 13所示原料油 1 评价其加氢脱 硫活性。 催化剂装量 100 毫升 （ 78 ~ 86 克） ， 反应条件为反应温度 300或 3401：, 反应压力 3.2兆帕， 液时空速 3.0小时— 氢油体积 比 300, 不同反应温度下的评价结果列于表 14- 16中。
对比例 12~ 16
下面的对比例说明参比催化剂的加氢脱硫活性。
按实例 53- 78 的方法评价催化剂的加氢脱硫活性， 不同的只是 所用催化剂为参比催化剂 Bi- B^ 评价结果列于表 17中。 表 13
原料油编号 原料油 1 原料油 2 原料油名称 常二线煤油 催化裂化柴油 密度， 克 /毫升 0. 8399 0. 9031 破含量， ppm 11000 2536 氮含量， ppm 58. 4 1901 碱性氮含量， ppm 22 402 胶质含量， 22毫克八 00毫 22 44. 4 升
苯胺点， 58. 4 38. 9 表 14
Figure imgf000032_0001
Figure imgf000033_0001
表 16
Figure imgf000033_0002
表 17
Figure imgf000034_0001
实例 79- 104
下面的实例说明本发明提供的催化剂的加氢脱硫和脱氮活性。 将得到的条形催化剂 ~(26分别截成长度为 2-3 毫米的条， 在
100毫升固定床加氢反应装置上用表 13所示原料油 2评价其加氢脱 硫和脱氮活性。催化剂装量 100毫升，反应条件为反应温度 320和 350 , 液时空速为 2小时— 氢油体积比 350。 不同反应温度下的评价 结果列于表 18~ 20中。
对比例 17~ 21
下面的对比例说明参比催化剂的加氢脱硫活性。
按实例 79~ 104 的方法评价催化剂的加氢脱硫和脱氮活性， 不 同的只是所用催化剂为参比催化剂 Bi- B^ 不同反应温度下的评价 结果列于表 21中„
表 18
实例编号 催化剂编号 脱疏率， 重％ 脱氮率， 重％
320X 3501： 320^ 350
79 78. 3 88. 0 35. 8 44. 9
80 c2 77. 0 87. 1 34. 2 43. 8
81 c3 76. 2 86. 9 34. 7 44. 6
82 c4 79. 0 87. 4 35. 6 」 44. 9
83 c5 76. 0 86. 4 36. 3 45. 1
84 c6 76. 3 86. 7 36. 8 45. 4
85 c7 78. 5 87. 8 34. 4 43. 2
86 c8 79. 0 87. 4 33. 8 43. 4 表 19
实例编号 催化剂编号 脱疏率， 重％ 脱氮率， 重％
320 350 X 320 " 350X
87 c9 76. 5 86. 3 35. 3 44. 2
88 Cio 79. 3 87. 8 36. 0 44. 6
89 77. 8 36. 4 44. 7
90 c12 76. 4 86. 2 35. 0 43. 9
91 ◦13 76. 5 85. 9 33. 5 43. 6
92 77. 5 86. 4 35. 2 44. 0
93 77. 0 86. 1 36. 7 45. 6
94 Cl6 78. 3 87. 2 34. 7 44. 0
95 C17 76. 2 86. 5 35. 3 44. 3
表 20
Figure imgf000036_0001
实例 105~ 140
下面的实例说明本发明提供的催化剂的甲苯饱和加氢活性。
以 50 重％甲苯的正己烷溶液为原料， 在小型固定床反应装置上 评价催化剂（ （26的甲苯饱和加氢活性， 催化剂装量 1.0克， 在 300 氢气气氛下用 3 重％二硫化碳的环己烷溶液预硫化 2 小时， 然后 通入反应原料， 反应温度 360 , 压力 4.1兆帕， 重时空速 3.4小时 一1，氢油体积比 400，反应 3 小时后取样， 反应产物用气相色谱在线分 析， 反应结果列于表 22- 24中。
对比例 22 ~ 26 本例说明对比例制备的催化剂的甲苯饱和加氢性能。
按实例 105 - 140 的条件评价催化剂的活性不同的只是所用催化 剂为参比催化剂 B5, 评价结果列于表 25中。
表 22
实例编号 催化剂编号 甲苯转化率， 重％
105 36. 3
106 c2 34. 4
107 c3 35. 0
108 c4 36. 2
109 c5 36. 5
120 c6 36. 4
121 c7 33. 8
122 c8 35. 2 表 23
Figure imgf000037_0001
Figure imgf000038_0001
表 25
实例编号 催化剂编号 甲笨转化率， 重％ 对比例 22 29. 8 对比例 23 B2 28. 9 对比例 24 B3 28. 3 对比例 25 B4 26. 3 对比例 26 B5 31. 1

Claims

权 利 要 求
1.一种镏分油加氢精制催化剂， 该催化剂含有一种氧化铝载体 和负载在该氧化铝载体上的至少一种第 VIB 族金属和 /或氧化物及至 少一种第 VIII 族金属和 /或氧化物； 其特征在于， 所述氧化铝载体 的孔容不小于 0. 35 毫升 /克， 孔直径为 40 - 100 埃孔的孔容占总孔 容的 80 %以上， 它采用如下方法中的一种或两种制备：
第一种方法， 其包括以下步骤：
1) 在温度 10 ~ 100 X， pH值为 6 ~ 9. 5的条件下， 使偏铝酸钠 或铝酸钠与选自硫酸铝， 硝酸铝， 氯化铝， 硝酸和疏酸溶液中的 一种或几种接触进行一次成胶反应；
2) 在 pH值为 9. 0 ~ 10. 5的条件下， 使步骤 1 ) 的反应产物与选 自碱金属的碳酸盐， 碱金属的碳酸氢盐与氨水的混合溶液， 碳酸 铵和碳酸氢铵中的一种或几种进行二次成胶反应；
3) 老化步骤 2)得到的氢氧化铝， 将固体和液体分离， 洗涤， 干燥并焙烧得到的固体产物，
和
第二种方法， 其包括以下步骤：
1) 在温度为 10 ~ 100 ：， pH值为 6 ~ 9. 5的条件下， 使偏铝酸 钠或铝酸钠与含二氧化碳的气体接触进行成胶反应， 成胶反应的 时间少于 40分钟；
2) 成胶反应结束后立即加入碱性物质； 使浆液的 pH值上升至 9. 5以上或立即进行固液分离并洗涤；
3) 老化步骤 2)得到的氢氧化铝， 将固体和液体分离， 洗涤， 干燥并焙烧得到的固体产物。
2.根据权利要求 1所述的催化剂， 其特征在于， 方法 1中所迷 偏铝酸钠或铝酸钠溶液的浓度为 30 - 300克氧化铝 /升， 硫酸铝、 硝酸铝和氯化铝的浓度为 10 - 120克氧化铝 /升， 硝酸和硫酸溶液 的浓度为 5 ~ 15重％。
3.根据权利要求 1所述的催化剂， 其特征在于， 方法 1中所述 一次成胶反应的 pH值为 6 ~ 9, 成胶反应的温度为 30 - 90 , 二次 成胶的 pH值为 9. 5 ~ 10. 5。
4. 根据权利要求 1所述的催化剂， 其特征在于， 按方法 1或 2 制备氧化铝载体时， 在干燥之前有一个成型的步骤。
5.根据权利要求 1所述的催化剂， 其特征在于， 方法 2所述偏 铝酸钠或铝酸钠溶液的浓度为 5 ~ 200克氧化铝 /升。
6.根据权利要求 5所述的催化剂， 其特征在于， 所述偏铝酸钠 或铝酸钠溶液的浓度为 5 ~ 120克氧化铝 /升。
7.根据权利要求 1所述的催化剂， 其特征在于， 方法 2所述含 二氧化碳的气体是纯的二氧化碳气体， 或者是由二氧化碳和不影 响反应的惰性气体组成的混合气体。
8.根据权利要求 1所述的催化剂， 其特征在于， 方法 2所述含 二氧化碳的气体中二氧化碳的含量不小于 5体积％。
9.根据权利要求 8所述的催化剂， 其特征在于， 所述含二氧化 碳的气体中二氧化碳的含量不小于 20体积 %。
10.根据权利要求 1所述的催化剂， 其特征在于， 方法 2中加入 碱性物质后， 使浆液的 pH值迅速上升到 9. 5 ~ 11. 5。
11.根据权利要求 1所述的催化剂， 其特征在于， 方法 2中所述 碱性物质选自无机碱、 有机碱和它们水溶液中的一种或几种。
12.根据权利要求 11所述的催化剂， 其特征在于， 所述无机碱 选自碱金属的氢氧化物、 偏铝酸盐、 碳酸盐、 碳酸氢盐、 碳酸铵、 氨水及它们的水溶液中的一种或几种； 所述有机碱选自水溶性胺 类、 脲、 吡啶及它们的水溶液中的一种或几种。
13.根据权利要求 12所述的催化剂， 其特征在于， 所述有机碱 选自溶于水的脂肪族胺类、 烃基氢氧化铵、 尿素、 吡啶及它们的 水溶液中的一种或几种。
14.根据权利要求 13所述的催化剂， 其特征在于， 所述有机碱 选自甲胺、 乙胺、 丙胺、 丙二胺、 丁胺的各种异构体、 戊胺的各 种异构体、 四乙基氢氧化铵、 尿素、 吡啶及它们的水溶液中的一 种或几种。
15.根据权利要求 1所述的催化剂， 其特征在于， 所述第 VIB族 金属和 /或氧化物是铬、 钼、 钨金属和它们的氧化物中的一种或几种, 所述第 VIII 族金属和 /或氧化物是钴、 镍金属和它们的氧化物中的 一种或几种。
16.根据权利要求 15 所述的催化剂， 其特征在于， 所述第 VIB 族金属和 /或氧化物是钨和 /或其氧化物， 所述第 VIII 族金属和 /或 氧化物是镍和 /或其氧化物， 以催化剂总量为基准并以氧化物计， 所 述第 VIB族金属的含量为 12 - 35 重％, 所述第 VIII族金属的含量 为 1 ~ 5 重％„
17.根据权利要求 1 所述的催化剂， 其特征在于， 以催化剂总量 为基准， 催化剂还含有 1 - 9 重％的氟。
18.权利要求 1所述催化剂的制备方法， 包括用含第 VIB族和第 VII I 族金属的水溶液浸渍催化剂载体， 浸渍后干燥并焙烧， 其中所 述催化剂载体为权利要求 1所述方法 1和 /或方法 2制备的氧化铝载 体。
19.根据权利要求 18所述的方法， 其特征在于， 在用含第 VIB 族和第 VIII族金属的水溶液浸渍催化剂载体之前， 先用含氟水溶液 浸渍催化剂载体， 干燥并焙烧。
20.根据权利要求 18或 19所述的方法， 其特征在于， 用含第 VIB 族和第 VIII族金属的水溶液浸渍催化剂载体或用含氟水溶液浸渍催 化剂载体之后的焙烧温度分别为 400 - 600X , 焙烧时间为 1 8 小 时。
21.—种适合用作馏分油加氢精制催化剂的氧化铝载体， 其特征 在于， 该氧化铝载体的孔容不小于 0. 35毫升 /克， 孔直径为 40 - 100 埃孔的孔容占总孔容的 80 %以上， 它采用如下方法中的一种或两种 制备：
第一种方法， 其包括以下步骤： 1) 在温度 10~ 100" , pH值为 6~ 9.5的条件下， 使偏铝酸钠 或铝酸钠与选自硫酸铝， 硝酸铝， 氯化铝， 硝酸和硫酸溶液中的 一种或几种接触进行一次成胶反应；
2) 在 pH值为 9.0~ 10.5的条件下， 使步骤 1)的反应产物与选 自碱金属的碳酸盐， 碱金属的碳酸氢盐与氨水的混合溶液， 碳酸 铵和碳酸氢铵中的一种或几种进行二次成胶反应；
3) 老化步骤 2)得到的氢氧化铝， 将固体和液体分离， 洗涤， 干燥并焙烧得到的固体产物，
第二种方法， 其包括以下步骤：
和
1) 在温度为 10- 100Ό, pH值为 6 ~ 9.5的条件下， 使偏铝酸 钠或铝酸钠与含二氧化碳的气体接触进行成胶反应， 成胶反应的 时间少于 40分钟；
2) 成胶反应结束后立即加入碱性物质； 使浆液的 PH值上升至 9.5以上或立即进行固液分离并洗涤；
3) 老化步骤 2)得到的氢氧化铝， 将固体和液体分离， 洗涤， 干燥并焙烧得到的固体产物。
22.权利要求 21所述氧化铝载体的制备方法。
PCT/CN2000/000318 1999-10-14 2000-10-13 Catalyseur d'hydroraffinage de distillat, son milieu et sa preparation WO2001026805A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN00802168A CN1124890C (zh) 1999-10-14 2000-10-13 一种馏分油加氢精制催化剂、其载体及制备
AU78986/00A AU7898600A (en) 1999-10-14 2000-10-13 Catalyst for hydrorefining distillate oil, its carrier and preparation thereof
EP00969164A EP1142637B1 (en) 1999-10-14 2000-10-13 Catalyst for hydrorefining distillate oil, its carrier and preparation thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN99121916.3 1999-10-14
CN99121916 1999-10-14

Publications (1)

Publication Number Publication Date
WO2001026805A1 true WO2001026805A1 (fr) 2001-04-19

Family

ID=5282190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2000/000318 WO2001026805A1 (fr) 1999-10-14 2000-10-13 Catalyseur d'hydroraffinage de distillat, son milieu et sa preparation

Country Status (8)

Country Link
US (1) US6518219B1 (zh)
EP (1) EP1142637B1 (zh)
KR (1) KR100633881B1 (zh)
CN (1) CN1124890C (zh)
AU (1) AU7898600A (zh)
MY (1) MY124770A (zh)
SA (1) SA00210628B1 (zh)
WO (1) WO2001026805A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769124A (zh) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 加氢处理催化剂的制备方法

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1473082B1 (en) * 2002-02-06 2013-10-09 JX Nippon Oil & Energy Corporation Method for preparing a hydroraffination catalyst
WO2005065823A1 (ja) * 2004-01-09 2005-07-21 Nippon Oil Corporation 石油系炭化水素の水素化脱硫触媒および水素化脱硫方法
JP4313265B2 (ja) * 2004-07-23 2009-08-12 新日本石油株式会社 石油系炭化水素の水素化脱硫触媒および水素化脱硫方法
TWI432381B (zh) * 2005-12-12 2014-04-01 Grace W R & Co 氧化鋁粒子
DE102007011471B4 (de) * 2006-03-09 2021-09-30 Shell Internationale Research Maatschappij B.V. Katalysatorkombination für die hydrierende Verarbeitung von Vakuumgasölen und/oder Visbreakergasölen
CN102259900B (zh) * 2010-05-24 2014-10-29 中国石油化工股份有限公司 一种水合氧化铝及其制备方法
DE102010021792B4 (de) * 2010-05-27 2022-03-31 Clariant Produkte (Deutschland) Gmbh Katalysatoren und Verfahren zu deren Herstellung
US9852176B2 (en) * 2010-09-03 2017-12-26 Vocus, Inc. Dynamic gathering of social media content
US9657236B2 (en) 2012-03-31 2017-05-23 China Petroleum & Chemical Corporation Process for hydrotreating heavy raw oils
CN104588123B (zh) * 2013-11-03 2017-01-11 中国石油化工股份有限公司 加氢裂化催化剂载体的制法
CN104588073B (zh) * 2013-11-03 2017-01-25 中国石油化工股份有限公司 一种加氢脱芳烃催化剂及其制备方法
CN105214667B (zh) * 2014-05-27 2017-10-03 中国石油化工股份有限公司 一种壳层分布催化剂及其制备方法和应用
CN105363446B (zh) * 2014-08-25 2019-06-14 中国石油化工股份有限公司 一种石脑油重整催化剂及制备方法
KR102504661B1 (ko) * 2017-08-18 2023-02-27 차이나 페트로리움 앤드 케미컬 코포레이션 중질 방향족 화합물로 경질 방향족 화합물을 제조하기 위한 촉매 및 이의 제조 방법과 용도
CN111097458B (zh) * 2018-10-25 2022-06-07 中国石油化工股份有限公司 一种加氢脱金属催化剂及其制法
CN111744483B (zh) * 2019-03-28 2021-09-07 中国石油化工股份有限公司 一种氧化铝、其制备方法及应用
CN110451541A (zh) * 2019-08-05 2019-11-15 中海油天津化工研究设计院有限公司 一种混合氢氧化铝的制备方法
RU2713903C1 (ru) * 2019-11-05 2020-02-11 Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" Способ получения переосажденного гидроксида алюминия и способ получения гамма-оксида алюминия на его основе
CN111823678A (zh) * 2020-07-17 2020-10-27 枣庄市聚信新材料科技有限公司 一种基于聚乙烯醇的农药缓释膜及其制备方法
CN114506866B (zh) * 2020-10-29 2023-07-28 中国石油化工股份有限公司 一种连续制备含硅拟薄水铝石的制备方法
CN114506869B (zh) * 2020-10-29 2023-09-01 中国石油化工股份有限公司 一种拟薄水铝石及其制备方法和应用
CN116328819B (zh) * 2021-12-17 2024-08-13 中国石油天然气股份有限公司 一种低生焦催化裂化催化剂的制备方法
CN117004434A (zh) * 2022-04-27 2023-11-07 中国石油化工股份有限公司 一种生产航煤的加氢处理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2932648A1 (de) * 1978-08-15 1980-02-21 Chiyoda Chem Eng Construct Co Verfahren zur herstellung eines fuer die verwendung als katalysatortraeger geeigneten aluminiumoxids und das dabei erhaltene produkt
FR2550099A1 (fr) * 1983-08-04 1985-02-08 Nikki Universal Co Ltd Procede de preparation d'alumine destinee a etre utilisee comme support de catalyseur
EP0147167A2 (en) * 1983-12-22 1985-07-03 Aluminum Company Of America Continuous process for neutralization of aluminate solution to form gels and appartatus therefor
CN85100161A (zh) * 1985-04-01 1986-07-30 山东省铝厂 碳酸化工艺(co2法)生产拟薄水铝石
CN1068975A (zh) * 1992-08-17 1993-02-17 中国石油化工总公司 低密度、大孔容、高强度氧化铝载体的制备方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL227115A (zh) 1957-05-17
US3268295A (en) * 1961-10-06 1966-08-23 Reynolds Metals Co Alumina hydrate and its method of preparation
US3779903A (en) 1967-12-11 1973-12-18 Shell Oil Co Hydroconversion process with a catalyst having a hydrogenation component composited with a high density alumina
US3539468A (en) * 1968-10-25 1970-11-10 Catalysts & Chem Inc Alumina hydrate compositions
US3876680A (en) * 1972-07-14 1975-04-08 Gulf Research Development Co Catalyst for the hydrogenation of aromatics
US4371513A (en) 1977-03-25 1983-02-01 W. R. Grace & Co. Alumina compositions
FR2398540A1 (fr) * 1977-07-29 1979-02-23 Raffinage Cie Francaise Procede de preparation d'alumines a porosite controlee et applications des alumines ainsi preparees
US4116882A (en) * 1977-12-14 1978-09-26 Continental Oil Company Method for the formation of alumina spheres
US4145316A (en) * 1977-12-27 1979-03-20 Exxon Research & Engineering Co. Preparation of catalysts of predetermined pore size distribution and pore volume
CA1143712A (en) 1979-06-05 1983-03-29 Gerard T. Pott Process for the preparation of a sulphided fluorine-containing nickel-tungsten catalyst and a process for the conversion of hydrocarbons, and the resulting hydrocarbons
US4500444A (en) 1982-04-22 1985-02-19 Beekman Stewart M Process for preparing basic aluminum carbonate gels substantially free from foreign anions and fibrous colloidal alumina monohydrate of a boehmite crystal lattice structure
CN85104438B (zh) 1985-06-13 1986-08-06 中国石油化工总公司石油化工科学研究院 一种馏分油加氢精制催化剂
US4579729A (en) * 1985-07-05 1986-04-01 Shell Oil Company Wide pore alumina supports
US4900711A (en) * 1988-03-23 1990-02-13 Harshaw/Filtrol Partnership Hydrotreating catalyst
CA2093412C (en) * 1992-04-20 2002-12-31 Gerald Verdell Nelson Novel hydroconversion process employing catalyst with specified pore size distribution
US5565091A (en) * 1993-02-15 1996-10-15 Idemitsu Kosan Co., Ltd. Catalyst composition manufacturing method and sulfur-containing hydrocarbon hydrodesulfurization method using the same catalyst composition
US5800797A (en) * 1993-12-09 1998-09-01 Catalysts & Chemicals Industries Co., Ltd. Process for producing alumina and apparatus therefor
CN1036791C (zh) 1994-01-04 1997-12-24 中国石油化工总公司 一种馏分油加氢精制催化剂
CN1045461C (zh) * 1996-05-02 1999-10-06 中国科学院山西煤炭化学研究所 一种作催化剂载体用氧化铝的制备方法
JP2001503313A (ja) * 1996-06-28 2001-03-13 中国石油化工集団公司 蒸留油のハイドロファイニング触媒および製造方法
CN1057021C (zh) 1996-06-28 2000-10-04 中国石油化工总公司 一种馏分油加氢精制催化剂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2932648A1 (de) * 1978-08-15 1980-02-21 Chiyoda Chem Eng Construct Co Verfahren zur herstellung eines fuer die verwendung als katalysatortraeger geeigneten aluminiumoxids und das dabei erhaltene produkt
FR2550099A1 (fr) * 1983-08-04 1985-02-08 Nikki Universal Co Ltd Procede de preparation d'alumine destinee a etre utilisee comme support de catalyseur
EP0147167A2 (en) * 1983-12-22 1985-07-03 Aluminum Company Of America Continuous process for neutralization of aluminate solution to form gels and appartatus therefor
CN85100161A (zh) * 1985-04-01 1986-07-30 山东省铝厂 碳酸化工艺(co2法)生产拟薄水铝石
CN1068975A (zh) * 1992-08-17 1993-02-17 中国石油化工总公司 低密度、大孔容、高强度氧化铝载体的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769124A (zh) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 加氢处理催化剂的制备方法
CN103769124B (zh) * 2012-10-24 2015-12-16 中国石油化工股份有限公司 加氢处理催化剂的制备方法

Also Published As

Publication number Publication date
KR100633881B1 (ko) 2006-10-16
KR20010101214A (ko) 2001-11-14
AU7898600A (en) 2001-04-23
US6518219B1 (en) 2003-02-11
MY124770A (en) 2006-07-31
EP1142637A1 (en) 2001-10-10
SA00210628B1 (ar) 2006-11-06
EP1142637B1 (en) 2007-04-18
EP1142637A4 (en) 2004-09-15
CN1327398A (zh) 2001-12-19
CN1124890C (zh) 2003-10-22

Similar Documents

Publication Publication Date Title
WO2001026805A1 (fr) Catalyseur d'hydroraffinage de distillat, son milieu et sa preparation
JP4405148B2 (ja) 新規な細孔構造を有するアルミナ、その作製方法、およびアルミナから作成される触媒
US6429172B1 (en) Method of manufacturing pseudo-boehmite
JP3945854B2 (ja) 擬ベ−マイトアルミナの製造方法及びその擬ベ−マイトアルミナを用いる水素化脱硫触媒用担体の製造方法
JP2002363576A (ja) 重質炭化水素油の２段階水素化処理方法
JP2002363575A (ja) 重質炭化水素油の２段階水素化処理方法
GB2146633A (en) Process of preparing alumina for use as a catalyst carrier
JPH06104568B2 (ja) 大形孔隙を有するアルミナの製造方法
CN114522692B (zh) 重油加氢处理催化剂和重油加氢处理方法
CN108865239B (zh) 裂解汽油选择加氢方法
US3523912A (en) Preparation of multicomponent catalysts
GB2150852A (en) Hydrocarbon hydrotreatment process
CN108863706A (zh) 一种含炔碳四馏分的选择加氢方法
CN108865243B (zh) 一种碳四烷基化原料的预加氢处理方法
CN1045461C (zh) 一种作催化剂载体用氧化铝的制备方法
CN111068686B (zh) 一种由渣油加氢失活催化剂制备镍基催化剂的方法
CN105713657A (zh) 一种加氢裂化的方法
JPH0587298B2 (zh)
CN100467570C (zh) 一种烃类加氢处理催化剂的制备方法
JP2762368B2 (ja) 使用済流動接触分解触媒を利用した触媒の製法
CN110304644B (zh) 一种生产高纯高黏拟薄水铝石的方法
CN113680347A (zh) 一种加氢精制催化剂及其制备方法和在油品精制及调控芳环饱和度中的应用
JPH06296879A (ja) 水素化処理触媒およびその製造方法
CN105709845A (zh) 加氢裂化催化剂载体及其制备方法
CN110935460A (zh) 一种高选择性加氢脱硫催化剂及其制备方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 00802168.6

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 2000969164

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2001/805/CHE

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1020017007432

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2000969164

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020017007432

Country of ref document: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

WWG Wipo information: grant in national office

Ref document number: 1020017007432

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 2000969164

Country of ref document: EP