WO2002049963A1 - Compose de titane, solution aqueuse contenant du titane, et procede de production de cette derniere - Google Patents

Compose de titane, solution aqueuse contenant du titane, et procede de production de cette derniere Download PDF

Info

Publication number
WO2002049963A1
WO2002049963A1 PCT/JP2001/011098 JP0111098W WO0249963A1 WO 2002049963 A1 WO2002049963 A1 WO 2002049963A1 JP 0111098 W JP0111098 W JP 0111098W WO 0249963 A1 WO0249963 A1 WO 0249963A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
aqueous solution
containing aqueous
producing
compound
Prior art date
Application number
PCT/JP2001/011098
Other languages
English (en)
Japanese (ja)
Inventor
Tomoaki Hirano
Narinobu Kagami
Original Assignee
Idemitsu Kosan Co., Ltd.
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 Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to JP2002551471A priority Critical patent/JPWO2002049963A1/ja
Priority to AU2002222689A priority patent/AU2002222689A1/en
Publication of WO2002049963A1 publication Critical patent/WO2002049963A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data

Definitions

  • the present invention relates to a titanium compound, a hydrated titanium compound, a titanium-containing aqueous solution, a method for producing the same, a titanium-supported refractory inorganic oxide carrier, a method for producing the same, a catalyst for hydrotreating hydrocarbon oil, and a hydrocarbon using the catalyst. It relates to the oil production method. More specifically, the present invention relates to a titanium-containing aqueous solution suitable for uniformly supporting titanium on a refractory inorganic oxide carrier, a method for producing the titanium-containing solution easily and inexpensively, and a high dispersion using the titanium-containing aqueous solution.
  • the present invention relates to a method for producing a hydrocarbon oil. Background art
  • titanium oxide has specific activity in various reactions as a catalyst itself or a carrier of an active metal.
  • titanium oxide alone has poor moldability and a small specific surface area, it has been studied that titanium oxide is supported on a molded article of a refractory oxidized product such as alumina, rather than using titanium oxide alone as a carrier. Often.
  • Titanium oxide is supported on a refractory oxide shaped body (carrier) such as alumina by adjusting the solution to the amount that the carrier absorbs water and impregnating the carrier with a pore filling method or a large excess of solution.
  • a refractory oxide shaped body such as alumina
  • an aqueous solution containing only titanium (ion) as a metal and an organic titanium compound solution dissolved in an organic solvent are used. Since aqueous solutions containing titanium specifically hydrolyze, Strongly acidic substances such as titanium tetrachloride and titanium sulfate are known.
  • alkoxide compounds, acetyl acetonate compounds and the like are known as organic titanium compounds.
  • these compounds have the following disadvantages.
  • the aqueous solution of titanium tetrachloride / titanium sulfate is strongly acidic and difficult to handle, and is easily hydrolyzed. Therefore, it must be supported in an extremely low pH range of less than pH.
  • a titanium-containing aqueous solution such as titanium tetrachloride having a pH of less than HI
  • a hydrolysis reaction occurs rapidly when it comes into contact with the refractory oxide, and the titanium is uniformly supported on the refractory oxide.
  • the effect of titanium may not be remarkably exhibited.
  • chlorine ion persulfate ion may have a bad effect on the catalytic activity, and chlorine ion causes corrosion for industrial equipment, so it is preferable that chlorine ion is not included.
  • organic titanium compounds such as alkoxide compounds and acetyl acetonate compounds
  • organic titanium compounds are preferred because they do not contain chloride ions or sulfate ions, but are easily hydrolyzed even with a small amount of water. It has drawbacks.
  • titanium hydroxide precipitates, so that titanium is unevenly distributed outside the refractory oxide molded body.
  • such an organic titanium compound is expensive, and it is extremely economically difficult to apply a large amount of a required hydrocarbon oil to a hydrotreating catalyst.
  • the present invention provides a titanium-containing aqueous solution suitable for uniformly supporting titanium on a refractory inorganic oxide carrier, a method for easily and inexpensively producing the titanium-containing aqueous solution, Using a refractory inorganic oxide carrier that supports titanium in a highly dispersed manner, a highly active and low-cost hydrocarbon oil hydrotreating catalyst obtained by supporting an active metal on this carrier, and low sulfur using the catalyst It is an object of the present invention to provide a method for producing a hydrocarbon oil of the present invention. Disclosure of the invention
  • the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, while dissolving titanium raw materials such as titanium hydroxide, titanium hydrated oxide, and metallic titanium in water under specific conditions, By stabilizing titanium ions with a certain compound, a titanium-containing aqueous solution that dissolves well in water, is stable over a wide pH range, and has significantly reduced amounts of impurities such as sulfate ions and chloride ions is simple and inexpensive. Was obtained.
  • a refractory inorganic oxide carrier supporting titanium in a highly dispersed manner can be easily obtained. It has been found that a highly active and low-cost catalyst for hydrotreating hydrocarbon oils can be obtained by supporting the catalyst.
  • the present invention has been completed based on strong knowledge.
  • A represents an ammonium salt, an alkali metal, an alkaline earth metal or a rare earth metal
  • B represents a hydroxycarboxylic acid group
  • X represents any numerical value in the range of 0.5 to 4.
  • Y indicates any numerical value in the range of 0.2 to 2
  • Z indicates any numerical value in the range of 0.2 to 2.
  • a hydrous titanium compound represented by the chemical formula Ax [Ti (O) y (B) z], wherein A represents an ammonium salt, an alkali metal, an alkaline earth metal or a rare earth metal, Represents a hydroxycarboxylic acid group, X represents any numerical value in the range of 0.5 to 4, y represents any numerical value in the range of 0.2 to 2, and Z represents 0.2 to 2 to Show any number in the range of 2.
  • a titanium hydroxide and / or a titanium hydrate are dissolved in water in a pH range of 7.0 to 14.0, and a titanium ion is reacted with a hydroxycarboxylic acid.
  • the titanium-containing aqueous solution according to the above (6) or (7), or the titanium-containing aqueous solution obtained by the method according to any one of the above (8) to (12) is brought into contact with a refractory inorganic oxide carrier. Titanium-supported refractory inorganic oxide carrier obtained by,
  • the titanium-containing aqueous solution according to (6) or (7) or the titanium-containing aqueous solution obtained by the method according to any of (8) to (12) is contacted with a refractory inorganic oxide carrier.
  • a method for producing a titanium-carrying refractory inorganic oxide carrier is contacted with a refractory inorganic oxide carrier.
  • the titanium-supported refractory inorganic oxide support obtained in (13) above contains at least a member selected from metals belonging to Groups 6, 8, 9 and 10 of the periodic table.
  • a catalyst for hydrotreating hydrocarbon oils carrying a kind of metal
  • Hydrocarbon oil having a boiling point of 140 to 400 is hydrotreated using the hydrotreating catalyst according to (15) to produce a hydrocarbon oil having a sulfur content of 5 Ow tp pm or less.
  • FIG. 1 is a UV-VIS spectrum of the titanium-containing aqueous solution obtained in Example 3.
  • FIG. 2 is a UV-VIS spectrum of the titanium-containing aqueous solution obtained in Example 4.
  • FIG. 3 is a UV-VIS spectrum of the titanium-containing aqueous solution obtained in Example 5.
  • FIG. 4 is a UV-VIS spectrum diagram of the titanium sulfate aqueous solution obtained in Comparative Example 4.
  • FIG. 5 is a chart showing the results of EPMA analysis of the titania-supported alumina carrier obtained in Example 7.
  • FIG. 6 is a chart showing the results of EPMA analysis of the titania-supported alumina carrier obtained in Example 8.
  • FIG. 7 is a chart showing an EPMA analysis result of the titania-supported alumina carrier obtained in Example 9.
  • FIG. 8 is a chart showing the results of an EPMA analysis of the titania-supported alumina carrier obtained in Comparative Example 6. BEST MODE FOR CARRYING OUT THE INVENTION
  • the titanium compound of the present invention is a titanium compound represented by the chemical formula Ax [Ti (O) y (B) z]. Further, it is a hydrous titanium compound represented by the chemical formula Ax [Ti (O) y (B) z].
  • the hydrated titanium compound includes those in which the titanium compound contains water molecules.
  • A represents an ammonium salt, an alkali metal, an alkaline earth metal or a rare earth metal.
  • A can be used to effectively support only the necessary titanium on the catalyst body during catalyst preparation and can be easily removed by operations such as drying and calcining. Is preferably used.
  • B is a hydroxycarboxylic acid.
  • Hydroxycarboxylic acid refers to a compound having one or more OH groups and two or more COOH groups in one molecule. If the number of ligands, such as OH groups and COOH groups, is small, it will dissolve well in water, making it impossible to prepare a stable titanium compound over a wide pH range.
  • B is preferably a hydroxycarboxylic acid having 12 or less carbon atoms, more preferably 8 or less carbon atoms. If the number of carbon atoms is too large, it is difficult to dissolve in water, while if the number of carbon atoms is too small, it is difficult to contribute to the stabilization of the titanium compound when it is made into an aqueous solution. Become. Suitable examples include cunic acid, tartaric acid, malic acid, lactic acid and the like.
  • X represents an arbitrary value in the range of 0.5 to 4, preferably 1.5 to 2.5, and y represents 0.2 to 2, preferably 0.5 to 1.5.
  • Z represents an arbitrary numerical value, and z represents an arbitrary numerical value in the range of 0.2 to 2, preferably 0.5 to 1.5. If the values of X, y, z are too large or too small, the stability of the aqueous solution will decrease.
  • the polymerization degree of T i is usually 1 to 50. More preferably, it is 1 to 10, more preferably 1 to 5. If the degree of polymerization is high, it is difficult to dissolve, so ideally a degree of polymerization of 1 is most preferable.
  • the titanium compound or hydrated titanium compound of the present invention can be produced by removing water from a titanium-containing aqueous solution produced by a method for producing a titanium-containing aqueous solution described below.
  • a method for producing a titanium-containing aqueous solution described below There is no particular limitation on the method of removing water, and it can be carried out by a method of drying under reduced pressure with or without heating. Alternatively, it can be performed by a freeze-drying method.
  • solids and crystals of a titanium-containing compound can be obtained by drying under normal pressure or reduced pressure for 0.5 to 48 hours under a condition of 50 or less. It can also be pulverized by grinding.
  • the titanium-containing aqueous solution according to the present invention is prepared from the above-mentioned titanium compound or hydrated titanium compound.
  • it is less than 50% by weight, more preferably less than 10% by weight.
  • a titanium-containing aqueous solution of 5% by weight or less, or even 2% by weight or less.
  • a titanium-containing aqueous solution is used as a raw material for preparing a catalyst, if the amount of impurities is too large, unnecessary substances are contaminated, so that titanium is diluted and the effect of the presence of titanium is significantly reduced.
  • Specific impurities include sulfate ions and chloride ions, which have the disadvantage that their presence reduces safety and increases corrosivity.
  • the amount of peroxide present in the titanium-containing aqueous solution is preferably 0.25 mol or less, more preferably 0.1 mol or less, based on 1 mol of Ti. If the amount of peroxide exceeds 0.25 mol, the stability of the titanium-containing aqueous solution will be impaired, and the titanium compound will be degraded. There is also a problem that the performance of) is not fully exhibited, and the decomposition of peroxide generates oxygen, increasing the internal pressure of the preservation solution and possibly damaging the container. Furthermore, when touched, there is a risk of injury to the hand, which is a problem in handling.
  • Redox titration is used as a method for determining peroxide (o 2 ) 2 —. Specifically, 5 ml of a 10% aqueous sulfuric acid solution and 1 Oml of a 10% aqueous potassium iodide solution were added to about 1 g of a titanium-containing aqueous solution, and iodine ions were oxidized to iodine with peroxide. A titration method using a 1 N aqueous sodium thiosulfate solution is used.
  • the titanium-containing aqueous solution according to the present invention contains titanium hydroxide and Z or titanium hydrate, ammonia, hydrogen peroxide and hydroxycarboxylic acid, and has a wavelength of 400 nm with respect to a wavelength of 360 nm. And 450 nm Extinction coefficient ratio E More than 0.05. If the molar extinction coefficient ratio E is less than 0.05, the complexation of titanium ions is insufficient, and the stability of the titanium-containing aqueous solution decreases. It is particularly preferable that the molar extinction coefficient ratio ⁇ is 0.07 or more.
  • the molar absorption coefficient ratio ⁇ is calculated by the following equation.
  • the molar extinction coefficient at 400 nm and ⁇ 440 nm indicate the molar extinction coefficient at a wavelength of 450 nm.
  • the titanium-containing aqueous solution can be efficiently produced by the method of the present invention described below.
  • the method is characterized in that an alkali compound and hydrogen peroxide are added to a titanium raw material to dissolve titanium, and then hydroxycarboxylic acid is added. Specifically, in the presence of ammonia and hydrogen peroxide, titanium hydroxide and / or titanium hydrate are dissolved in water in the range of pH 7.0 to 14.0, and titanium ions are dissolved. By stabilizing with hydroxycarboxylic acid, a titanium-containing aqueous solution substantially free of chlorine or sulphate is obtained.
  • titanium raw material in the method for producing a titanium-containing aqueous solution of the present invention metals other than titanium and titanium hydroxide, titanium hydrate oxide, and titanium metal substantially free of anions such as chloride ions and sulfate ions are used. .
  • substantially no anion such as chloride ion is detected means that the anion content is T i
  • T i 0 2 reference sulfate ion content less 5% by weight is T i 0 2 reference sulfate ion content less, more preferably those of 2 wt% or less is preferably used.
  • content of ion sulfate in the titanium hydrated oxide is 5% by weight or less, when the titanium is supported on the refractory oxide, it can be regarded as substantially free of sulfate ions.
  • titanium metal can also be used.
  • the powder is preferably used because of the ease of dissolution.
  • Titanium hydroxide and titanium hydrated oxide may be used as a slurry, but dried ones may also be used. There is no particular limitation on the drying conditions, but the drying is carried out under general conditions, that is, under normal pressure or reduced pressure, at a temperature of 150 ° C. or less, which is appropriately selected.
  • T i 0 2 content is determined by weighing after removal of the water and calcined at 5 0 0. Moisture content, which was shown by a weight decrease ratio was measured at KET moisture meter (the maximum temperature 1 8 0), the remaining water was removed corresponds substantially T io 2.
  • a titanium-containing aqueous solution can be produced according to the following steps.
  • a titanium raw material such as the titanium hydroxide, titanium hydrate oxide, or titanium metal is dispersed in an aqueous medium to form a slurry.
  • the dispersibility can be improved by making the particles fine using a homogenizer or the like.
  • the slurry containing titanium hydroxide and / or titanium hydrate is subjected to pH 7.0 to 14.0, preferably pH 8.0 in the presence of an alkali compound, preferably ammonia and hydrogen peroxide. 0 to: Keep in the range of L3.0. As a result, most of the titanium raw material is dissolved.
  • the pH is adjusted mainly by the amount of the alkali compound added.
  • alkali compound not only ammonia but also general compounds can be used.
  • alkali metal, alkaline earth metal, rare earth metal hydroxides and the like can be used.
  • alkali metal hydroxides such as ammonia and sodium hydroxide are preferably used.
  • the temperature is not particularly limited, it is usually appropriate to treat the aqueous solution, that is, 5 to 80, more preferably 10 to 70. If the temperature is too low, the dissolution of the titanium raw material does not easily proceed. On the other hand, if the temperature is too high, decomposition reaction of hydrogen peroxide (oxygen release) occurs and not only the added hydrogen peroxide is wasted, but also the rupture of the dissolving tank may occur due to an increase in pressure.
  • alkali compound and the addition amount of hydrogen peroxide, and against the T i 0 2 1 mol, alkali compound is from 1.5 to 2 0 moles, as hydrogen peroxide is about 1.0 to 2 0 mole
  • add an alkaline compound and hydrogen peroxide solution respectively. If the added amount is too small, the titanium raw material is hardly dissolved, and even if it is added excessively, the effect of improving the dissolution reaction is hardly recognized.
  • the order of addition of the alkaline compound and the hydrogen peroxide solution is not particularly limited, and any addition may be made as long as the pH is set within the above range.
  • the general order of addition, including the hydroxy force / reponic acid described below, is as follows.
  • the aqueous solution obtained by previously mixing the alkali metal compound and the hydrogen peroxide solution and removing the heat is added little by little.
  • titanium raw material is dissolved by the action of hydrogen peroxide at pH 7 ⁇ l4, but hydrogen peroxide itself is easily decomposed even at low temperatures, and its decomposition is accelerated as the temperature rises . If the amount of heat removed is smaller than the amount of heat generated, the system temperature may rise and runaway may occur. Cooling is especially important when producing. However, even if the cooling capacity is not sufficient, by adding an appropriate amount of dilution water, the heat capacity of the system can be increased to mitigate the temperature rise and prevent runaway.
  • the dilution water mentioned here includes not only water added as water but also water contained in each of titanium raw material, ammonia water, and hydrogen peroxide.
  • the amount of the dilution water, to T i 0 2 equivalent as 1 part by weight of titanium emission material, usually 1 0 to: L 0 0 parts by weight, more preferably, 1 5-7 0 weight parts suitable is there. If the amount of dilution water is small, the temperature rises due to the heat generated by the decomposition of hydrogen peroxide, and there is a risk of runaway. Also, if the amount of dilution water added is too large, the concentration will decrease, making it difficult for the dissolution reaction to occur, and it will be time-consuming to concentrate to reach the target concentration.
  • hydroxycarboxylic acid is added in order to stabilize the titanium-containing aqueous solution obtained by dissolving the titanium raw material in this manner.
  • the hydroxycarboxylic acid may be added to the slurry before the operation of dissolving the titanium raw material, or may be added during or after the dissolution.
  • the hydroxycarboxylic acid those having two or more carboxyl groups and one or more hydroxyl groups in one molecule and being easily soluble in water are preferable.
  • the hydroxycarboxylic acid preferably has 12 or less carbon atoms, more preferably 8 or less carbon atoms. If the carbon number is too large, it is difficult to dissolve in water. On the other hand, if the carbon number is too small, when the titanium compound is made into an aqueous solution, it does not contribute to stabilization.
  • cunic acid, malic acid, tartaric acid, lactic acid and the like are preferably used.
  • the addition amount of the hydroxycarboxylic acid to T i 0 2 1 mole usually 0.2 to 2.0 moles.
  • the hydroxycarboxylic acid may be added as crystals (particles, powder) or in the form of an aqueous solution.
  • the temperature at which the hydroxycarboxylic acid is added is particularly limited. However, it is usually performed under the condition of 5 or less. More preferably, it is 0 to 40 or less. If the temperature is high, the decomposition of residual hydrogen peroxide occurs rapidly, which is not preferable.
  • the remaining hydrogen peroxide is removed by adding the hydroxycarboxylic acid and maintaining the temperature at a temperature of 10 to 95 with stirring for 0.5 to 48 hours.
  • a transparent and stable titanium-containing aqueous solution can be obtained.
  • the titanium-containing aqueous solution thus prepared is concentrated as an aqueous solution for titanium impregnation under normal pressure or reduced pressure under conditions similar to the hydrogen peroxide removal step, or at an optional concentration. Can be diluted. Furthermore, by removing water from the titanium-containing aqueous solution, a solid of the titanium-containing compound can be obtained.
  • the method of removing water is not particularly limited, and can be performed by a general method, that is, a method of drying and freeze-drying.
  • solids and crystals of a titanium-containing compound can be obtained by drying under ordinary pressure or reduced pressure for 0.5 to 48 hours under a condition of 50 or less. It can also be pulverized by grinding.
  • the titanium-containing aqueous solution prepared by the method of the present invention is stable in a wide range of pH range (2-12), titanium can be uniformly and highly supported on the refractory inorganic oxide.
  • the titanium-containing aqueous solution is safe because it is difficult to remove even if calcined, such as metals other than titanium, chloride ions, and sulfate ions, and does not substantially contain substances that may adversely affect the surface state of the catalyst. Certainly it is applicable for industrial use.
  • a titanium-containing refractory inorganic oxide carrier is produced by contacting the titanium-containing aqueous solution obtained as described above with a refractory inorganic oxide carrier.
  • the refractory inorganic oxide carrier used in this method includes o
  • alumina, silica, silica 'alumina, magnesia, zinc oxide, crystalline aluminosilicate, clay mineral, calcium oxide, oxide Vanadium, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, silver oxide, tin oxide, bismuth oxide, and mixtures thereof are preferably used.
  • the average pore diameter is preferably in the range of 5 to 15 nm.
  • the shape is not particularly limited, but a compact such as a powder, a cylinder, a three-leaf, or a four-leaf is preferably used.
  • Impregnation can be performed under normal pressure or reduced pressure by a general method such as a poiling method (impregnation method) or a method of immersing a carrier in a large excess of titanium aqueous solution.
  • the titanium-containing aqueous solution prepared by the method of the present invention is stable in the pH range of 2 to 12, and the pH can be adjusted by using a water solution or an organic acid. In general, in consideration of the state of surface hydroxyl groups, for example, it is preferable to support at pH 5 to 7 when supporting on alumina, and at pH 3 to 5 when supporting on silicon.
  • Supported amount of titanium, with Sani ⁇ (T i 0 2) standards, for the refractory inorganic oxide support preferably from 0.5 to 3 0 wt%, more preferably 1 to 1 5 wt% is there. If the supported amount is too small, the effect of the addition of the metal may not be sufficiently exhibited, and if the supported amount is too large, uneven deposition or aggregation on the carrier may occur. This is not preferable because sufficient effects cannot be obtained.
  • the carrier is treated by a general method such as drying and baking to obtain a titanium-carrying carrier.
  • the drying is usually performed at normal pressure or reduced pressure, preferably at a temperature of 50 to 300, more preferably at a temperature of 100 to 120, for about 0.5 to about L00 hours.
  • baking is performed as necessary.
  • the firing temperature is preferably from 300 to 600 °, more preferably from 450 to 600, and the firing time is usually from about 0.5 to 100 hours.
  • the catalyst for hydrotreating hydrocarbon oils of the present invention comprises the titanium-supported refractory inorganic oxide carrier obtained as described above, and a group 6, 8, 9 or 10 of the periodic table. It can be prepared by supporting at least one metal selected from metals belonging to the group.
  • molybdenum, tungsten, and the like are used as Group 6 metals of the periodic table, and molybdenum is particularly preferably used.
  • molybdenum compound molybdenum trioxide, ammonium paramolybdate and the like are suitable.
  • tungsten compound tungsten trioxide, ammonium tungstate and the like are suitable.
  • the supported amount (on an oxide basis) is preferably 4 to 40% by weight, more preferably 8 to 35% by weight, based on the total amount of the catalyst.
  • cobalt or nickel is usually suitably used.
  • cobalt compound cobalt carbonate or cobalt nitrate is preferred, and as the Nigger compound, nickel carbonate / nickel nitrate is preferred.
  • the supported amount (on an oxide basis) is preferably 1 to 12% by weight, more preferably 2 to 10% by weight, based on the total amount of the catalyst.
  • a phosphorus compound can be supported, and as the phosphorus compound, Phosphorus pentoxide, orthophosphoric acid and the like are used.
  • the supported amount (on an oxide basis) is preferably 0.5 to 8% by weight, more preferably 1 to 6% by weight, based on the total amount of the catalyst.
  • the above active metal compound is usually supported by an impregnation method.
  • the phosphorus compounds may be separately impregnated with the above Group 6 and Group 8-10 metals, but it is efficient to carry them out simultaneously.
  • the above-mentioned metal compounds are preferably 0.7 to 7.0 mol / l for group 6 metals, 0.3 to 3.6 mol l for group 8 to 10 metals, and 0 to 2.2 mol for phosphorus compounds. It is preferable that the titanium-supported carrier is dissolved in pure water at a ratio of mol liters, adjusted to have an equivalent water absorption, and then impregnated.
  • the pH at the time of impregnation is generally 1 to 4, preferably 1.5 to 3.5 in the acidic region, and 9 to 12 in the alkaline region, preferably 10 to 1 in the alkaline region. Is one.
  • the pH can be adjusted using an organic acid, ammonia, or the like.
  • a water-soluble organic compound such as polyethylene glycol having a molecular weight of 90 to 1000 to the impregnating liquid stabilized with a phosphorus compound.
  • the amount added is preferably 2 to 20% by weight, more preferably 3 to 15% by weight, based on the carrier.
  • heat treatment is usually performed.
  • any method may be used, in which the heat treatment is performed every time the impregnation is performed, or the heat treatment is not performed. It is advantageous to carry out the heat treatment in air, usually at 550 or less, for about 3 to 16 hours.
  • the catalyst of the present invention thus prepared is used as a catalyst for hydrotreating hydrocarbon oils.
  • All petroleum fractions can be used as the hydrocarbon oil to be treated using the above catalyst.
  • kerosene, light gas oil, heavy gas oil, cracked gas oil, etc. Oil, decompression residual oil, asphaltene oil, tar sands Oils and the like can be mentioned.
  • the catalyst of the present invention is particularly useful as a hydrotreating catalyst for an ultra-deep degassing region of a light gas oil fraction (sulfur content: 5 Oppm or less). That is, in detail, the above-mentioned hydrotreating catalyst is obtained by hydrotreating a carbon dioxide oil having a boiling point of 140 to 400 ⁇ , so that the sulfur content is 5 Owt ppm or less, preferably 3 Ow tp pm or less. It is preferably used for producing a hydrocarbon oil of 20 wt ppm or less, more preferably 10 wt ppm or less.
  • the conditions for hydrotreating such a fraction are the same as for ordinary hydrotreating, for example, a reaction temperature of 250 to 4003 ⁇ 4, a reaction pressure of 2 to: L OMPa, and a hydrogen / feed oil ratio of 50 to 500 Nm 3.
  • Z kiloliters, liquid hourly space velocity (LH SV) can be treated with 0. 2 ⁇ 5. 0 h 1.
  • T i Measured using a commercially available ICP device (emission spectroscopy).
  • the residual hydrogen peroxide concentration of the titanium-containing aqueous solution was measured by a redox titration method (potassium iodide method).
  • the amount of residual hydrogen peroxide was 0.03 mol with respect to 1 mol of Ti.
  • the measured Anion concentration impurity using a commercially available anion chromatography graph apparatus, impurities (mainly S0 4) was 1. 9w t% to T I_ ⁇ 2.
  • the solution was kept at a temperature of 30 ° C. or less for 6 hours, and then kept at 80 to 95 for 12 hours to obtain 120 g of a transparent titanium-containing aqueous solution having a pH of 6.2. Further, this compound was dried under reduced pressure under the condition of 30 to obtain a powder.
  • titanium tetrachloride and 1 liter of pure water were cooled with ice. Pure water is stirred, and titanium tetrachloride is gradually added dropwise while cooling, and colorless
  • a titania sol hydrochloric acid solution To this titania solution, 1.2 times equivalent of aqueous ammonia (concentration: 1 mol / l) was added dropwise and stirred for 1 hour to obtain a titanium hydroxide gel.
  • This titanium hydroxide gel was separated by suction filtration, redispersed in about 1 liter of pure water, and washed by filtration. This operation was repeated 4 to 5 times until the washing solution became neutral, and it was confirmed that the solution was free of chlorine ion using silver nitrate.
  • FIG. 1 shows the UV-VIS spectrum of the titanium-containing aqueous solution (A1).
  • the titanium-containing aqueous solution (A1) had a strong absorption spectrum in the ultraviolet, and was stable over a wide range of pH 2 to 13 for a long period of time.
  • FIG. 2 shows the UV-VIS spectrum of the titanium-containing aqueous solution (A2).
  • the titanium-containing aqueous solution (A2) had a strong absorption spectrum in the ultraviolet and was stable over a wide range of pH from 2 to 13 over a long period of time.
  • FIG. 3 shows the UV-VIS spectrum of this titanium-containing aqueous solution (A3).
  • the titanium-containing aqueous solution (A3) had a strong absorption spectrum in the ultraviolet, and was stable for a long time in a wide pH range of 2 to 13.
  • Fig. 4 shows the UV-VIS spectrum of this titanium sulfate aqueous solution (A4).
  • the aqueous solution of titanium sulfate (A4) has a very strong absorption spectrum in the ultraviolet.
  • Tan powder Hydrogen peroxide 6 1 mol-reduced but not dissolved.
  • the titanium oxide (Ti 0 2 ) ratio determined by calcining at 500 for 4 hours is 85 wt%, and the titanium oxide hydroxide powder is 16. O kg, 320 kg pure water and 26 ammonia water 3 3. 5 kg of weight 0/0, and charged to the reactor having an internal volume of 0. 5 m 3, was stirred and slurried cooled. Next, 99.2 kg of 35% by weight hydrogen peroxide solution was added little by little over 1 hour so that the temperature of the hydrous titanium oxide slurry was maintained at 20. Thereafter, the mixture was stirred for 3 hours while maintaining the value of 20 to obtain a yellow-green transparent aqueous solution containing titanium.
  • the titanium oxide (Ti 0 2 ) ratio determined by calcining at 500 ° C for 4 hours is 85 wt%.
  • a reactor having an inner volume of 0.5 m 3 was charged with 33.5 kg of 6% by weight aqueous ammonia, stirred, slurried, and cooled.
  • 99.2 kg of a 35% by weight aqueous hydrogen peroxide solution was added little by little to the hydrous titanium oxide slurry.
  • the temperature of the aqueous solution could not be maintained at 20, and the temperature of the aqueous solution rose, so the addition rate of the mixed aqueous solution was reduced.
  • FIG. 5 shows the results of this EPMA analysis.
  • the titania-supported alumina support (B1) uniformly supports titania from outside to inside.
  • a titanium-containing aqueous solution (A2) was diluted with pure water to 80 milliliters, and 100 g of cylindrical ⁇ -alumina was impregnated with a pore volume of 0.8 milliliter / g under reduced pressure (pore filling method). After that, it was dried under vacuum at 70 for 1 hour, dried at 12 ⁇ for 3 hours, and finally calcined at 500 for 4 hours to obtain an alumina carrier (B2) supporting 5% by weight of titanium.
  • the obtained titania-supported alumina carrier (B2) (compact) was subjected to EPMA analysis in the diameter direction.
  • Figure 6 shows the analysis results of this EPMA.
  • the titania-supported alumina support (B 2) uniformly supports titania from outside to inside.
  • a titanium-containing aqueous solution (A3) 47 Miriritsutoru diluted with pure water and 80 ml, pore volume 0.8 ml y / g impregnated under vacuum in a cylindrical ⁇ - alumina 1 00 g (pore filling method) was . After that, it was dried under vacuum at 70 for 1 hour, dried at 120 for 3 hours, and finally calcined at 500 for 4 hours to obtain an alumina carrier (B3) supporting 5% by weight of titaurea.
  • the obtained titanium support (B 3) (formed body) was subjected to EPMA analysis in the diameter direction.
  • FIG. 7 shows the results of this EPMA analysis.
  • the titania-supported alumina support (B 3) uniformly supports titania from outside to inside.
  • the catalyst C2 was prepared by vacuum drying at 70 for 1 hour and heat-treating for 120 and 16 hours.
  • Table 4 shows the compositions of the catalysts prepared in Example 10 and Comparative Example 7.
  • the raw oil having the properties shown in Table 5 “Middle Eastern straight gas oil (LGO) J was circulated with hydrogen gas and pre-sulfurized.
  • the above-mentioned feed oil“ Middle East straight gas oil (LGO) was passed along with hydrogen gas to carry out a hydrodesulfurization reaction.
  • titanium is homogeneously supported on a refractory inorganic oxide carrier, which is stable in a wide range of pH, is substantially free of metals other than titanium, chloride ions, and sulfate ions.
  • a titanium-containing aqueous solution suitable for this can be easily and inexpensively produced.
  • this titanium-containing aqueous solution it is possible to provide a refractory inorganic oxide carrier that supports titanium in a highly dispersed state, and a highly active and low-cost catalyst for hydrotreating hydrocarbon oil. Further, by using such a catalyst, a hydrocarbon oil having a low sulfur content can be efficiently produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne (1) un composé de titane ou un composé de titane hydraté représenté par une formule chimique spécifique ; (2) une solution aqueuse contenant du titane, pouvant être utilisée pour déposer du titane de manière uniforme sur un support d'oxyde inorganique réfractaire ; (3) un procédé pour produire une solution aqueuse contenant du titane, consistant à ajouter un composé alcalin et du peroxyde d'hydrogène à un matériau de titane pour dissoudre le titane puis à ajouter un acide hydroxycarboxylique ; (4) ledit support ; (5) un catalyseur extrêmement actif pour l'hydrogénation d'une huile hydrocarbure, qui comprend le support et un métal spécifique supporté sur ce dernier ; et (6) un procédé pour produire une huile hydrocarbure à faible teneur en soufre, consistant à utiliser ledit catalyseur d'hydrogénation pour hydrogéner une huile hydrocarbure spécifique.
PCT/JP2001/011098 2000-12-19 2001-12-18 Compose de titane, solution aqueuse contenant du titane, et procede de production de cette derniere WO2002049963A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2002551471A JPWO2002049963A1 (ja) 2000-12-19 2001-12-18 チタン化合物、チタン含有水溶液及びその製造方法
AU2002222689A AU2002222689A1 (en) 2000-12-19 2001-12-18 Titanium compound, aqueous solution containing titanium, and process for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000385825 2000-12-19
JP2000-385825 2000-12-19

Publications (1)

Publication Number Publication Date
WO2002049963A1 true WO2002049963A1 (fr) 2002-06-27

Family

ID=18853029

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/011098 WO2002049963A1 (fr) 2000-12-19 2001-12-18 Compose de titane, solution aqueuse contenant du titane, et procede de production de cette derniere

Country Status (3)

Country Link
JP (2) JPWO2002049963A1 (fr)
AU (1) AU2002222689A1 (fr)
WO (1) WO2002049963A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005082619A (ja) * 2003-09-04 2005-03-31 Idemitsu Kosan Co Ltd 水素化処理触媒の予備硫化方法及び軽油の脱硫方法
JP2005179118A (ja) * 2003-12-19 2005-07-07 Toho Catalyst Co Ltd 四塩化チタン水溶液の製造方法
JP2007514632A (ja) * 2003-11-21 2007-06-07 ナショナル ユニバーシティ オブ アイルランド、 ゴールウエイ 可溶性金属酸化物および金属酸化物溶液
JP2008012501A (ja) * 2006-07-10 2008-01-24 Toyota Motor Corp ＮＯｘ吸蔵材の担持方法
JP2008178843A (ja) * 2007-01-26 2008-08-07 Idemitsu Kosan Co Ltd チタン担持耐火性無機酸化物担体、炭化水素油の水素化処理触媒及びそれを用いた水素化処理方法
JP2008247811A (ja) * 2007-03-30 2008-10-16 Denki Kagaku Kogyo Kk 低アンモニウム型チタンペルオキソ化合物の合成方法
JP2015131775A (ja) * 2014-01-10 2015-07-23 日立金属株式会社 高融点金属の非フッ酸系水溶液およびその製造方法
US9101914B2 (en) 2011-03-31 2015-08-11 Nissan Motor Co., Ltd. Exhaust gas purifying catalyst, exhaust gas purifying monolith catalyst, and method for manufacturing exhaust gas purifying catalyst
US9352301B2 (en) 2012-09-10 2016-05-31 Nissan Motor Co., Ltd. Exhaust gas purification catalyst, exhaust gas purification monolith catalyst, and method for producing exhaust gas purification catalyst
KR20190135025A (ko) * 2017-03-30 2019-12-05 제이엑스티지 에네루기 가부시키가이샤 탄화수소유의 수소화 탈황 촉매 및 수소화 탈황 촉매의 제조 방법

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102575175B (zh) 2009-09-30 2014-06-25 吉坤日矿日石能源株式会社 烃油用加氢脱硫催化剂、其生产方法和加氢精制的方法
JP5610874B2 (ja) * 2010-06-25 2014-10-22 Ｊｘ日鉱日石エネルギー株式会社 炭化水素油の水素化脱硫触媒及びその製造方法
US9061265B2 (en) 2010-06-25 2015-06-23 Jx Nippon Oil & Energy Corporation Hydrodesulfurization catalyst for hydrocarbon oil, process of producing same and method for hydrorefining
JP5610875B2 (ja) * 2010-06-25 2014-10-22 Ｊｘ日鉱日石エネルギー株式会社 炭化水素油の水素化精製方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0789722A (ja) * 1993-08-30 1995-04-04 Merck Patent Gmbh 二酸化チタンゾルの光安定化
JPH07108173A (ja) * 1993-10-15 1995-04-25 Idemitsu Kosan Co Ltd 水素化触媒製造用含浸液、水素化触媒の製造方法及び炭化水素油の水素化処理方法
JPH07328449A (ja) * 1994-06-13 1995-12-19 Idemitsu Kosan Co Ltd 重質炭化水素油の水素化転化用の触媒前駆体及びそれを用いる重質炭化水素油の水素化転化方法
JPH11278843A (ja) * 1998-01-27 1999-10-12 Nippon Parkerizing Co Ltd 酸化チタンゾルおよびその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04166231A (ja) * 1990-10-29 1992-06-12 Sumitomo Metal Mining Co Ltd 水素化処理用触媒の製造方法
JP3238349B2 (ja) * 1996-05-24 2001-12-10 日本パーカライジング株式会社 親水性、光触媒性および透光性に優れた酸化チタンセラミック塗料およびその製造方法
JP3821521B2 (ja) * 1996-10-22 2006-09-13 触媒化成工業株式会社 チタニア−アルミナ担体とその製造方法並びにそれを使用した水素化処理触媒
JP3385243B2 (ja) * 1998-01-27 2003-03-10 日本パーカライジング株式会社 酸化チタンゾルの製造方法
JP2000159786A (ja) * 1998-11-26 2000-06-13 Furuuchi Kagaku Kk 有機チタンペロキシ化合物、その製造方法、及びチタン含有複合酸化物の作製法
JP4916044B2 (ja) * 2000-04-25 2012-04-11 出光興産株式会社 炭化水素油の水素化処理触媒及び炭化水素油の水素化処理方法
JP3502904B2 (ja) * 2000-05-11 2004-03-02 岐阜大学長 チタン含有水溶液の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0789722A (ja) * 1993-08-30 1995-04-04 Merck Patent Gmbh 二酸化チタンゾルの光安定化
JPH07108173A (ja) * 1993-10-15 1995-04-25 Idemitsu Kosan Co Ltd 水素化触媒製造用含浸液、水素化触媒の製造方法及び炭化水素油の水素化処理方法
JPH07328449A (ja) * 1994-06-13 1995-12-19 Idemitsu Kosan Co Ltd 重質炭化水素油の水素化転化用の触媒前駆体及びそれを用いる重質炭化水素油の水素化転化方法
JPH11278843A (ja) * 1998-01-27 1999-10-12 Nippon Parkerizing Co Ltd 酸化チタンゾルおよびその製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005082619A (ja) * 2003-09-04 2005-03-31 Idemitsu Kosan Co Ltd 水素化処理触媒の予備硫化方法及び軽油の脱硫方法
JP2007514632A (ja) * 2003-11-21 2007-06-07 ナショナル ユニバーシティ オブ アイルランド、 ゴールウエイ 可溶性金属酸化物および金属酸化物溶液
JP2005179118A (ja) * 2003-12-19 2005-07-07 Toho Catalyst Co Ltd 四塩化チタン水溶液の製造方法
JP4553233B2 (ja) * 2003-12-19 2010-09-29 東邦チタニウム株式会社 四塩化チタン水溶液の製造方法
JP2008012501A (ja) * 2006-07-10 2008-01-24 Toyota Motor Corp ＮＯｘ吸蔵材の担持方法
JP2008178843A (ja) * 2007-01-26 2008-08-07 Idemitsu Kosan Co Ltd チタン担持耐火性無機酸化物担体、炭化水素油の水素化処理触媒及びそれを用いた水素化処理方法
JP2008247811A (ja) * 2007-03-30 2008-10-16 Denki Kagaku Kogyo Kk 低アンモニウム型チタンペルオキソ化合物の合成方法
US9101914B2 (en) 2011-03-31 2015-08-11 Nissan Motor Co., Ltd. Exhaust gas purifying catalyst, exhaust gas purifying monolith catalyst, and method for manufacturing exhaust gas purifying catalyst
US9352301B2 (en) 2012-09-10 2016-05-31 Nissan Motor Co., Ltd. Exhaust gas purification catalyst, exhaust gas purification monolith catalyst, and method for producing exhaust gas purification catalyst
JP2015131775A (ja) * 2014-01-10 2015-07-23 日立金属株式会社 高融点金属の非フッ酸系水溶液およびその製造方法
KR20190135025A (ko) * 2017-03-30 2019-12-05 제이엑스티지 에네루기 가부시키가이샤 탄화수소유의 수소화 탈황 촉매 및 수소화 탈황 촉매의 제조 방법
KR102537641B1 (ko) 2017-03-30 2023-05-31 에네오스 가부시키가이샤 탄화수소유의 수소화 탈황 촉매 및 수소화 탈황 촉매의 제조 방법

Also Published As

Publication number Publication date
JP2008239484A (ja) 2008-10-09
AU2002222689A1 (en) 2002-07-01
JPWO2002049963A1 (ja) 2004-04-22
JP5047050B2 (ja) 2012-10-10

Similar Documents

Publication Publication Date Title
JP5047050B2 (ja) チタン含有水溶液及びその製造方法
Ramirez et al. Fenton-like oxidation of Orange II solutions using heterogeneous catalysts based on saponite clay
Rezvani et al. Synthesis of new nanocomposite based on nanoceramic and mono substituted polyoxometalate, PMo11Cd@ MnFe2O4, with superior catalytic activity for oxidative desulfurization of real fuel
Rezvani et al. Synthesis of new nanocomposite based on ceramic and heteropolymolybdate using leaf extract of Aloe vera as a high‐performance nanocatalyst to desulfurization of real fuel
EP2069439B1 (fr) Particule nanocomposite et son processus de préparation
US20030187077A1 (en) Colloidal dispersion of a cerium compound or compound of cerium and at least one other element selected from rare earths and transition metals and comprising an amino acid
JP3251951B2 (ja) 表面積の大なるジルコニア
JP2001510132A (ja) モリブドタングステン酸ニッケル水素処理触媒
JP2005254240A (ja) 酸化およびアンモ酸化触媒を改良する方法
CN102639242B (zh) 可见光响应型氧化钛微粒分散体及其制备方法
CN110038620A (zh) 制备加氢裂化催化剂的方法
WO2010109823A1 (fr) Catalyseur d'hydroraffinage, son procédé de production et procédé d'hydroraffinage d'une huile hydrocarbonée
KR920007596B1 (ko) 개선된 형태학적 특성을 갖는 산화 제2세륨 및 그의 제조 방법
JP5212353B2 (ja) 可視光応答型酸化チタン系微粒子分散液およびその製造方法
JP5582999B2 (ja) アルミナコロイド含有水溶液の製造方法及び該製造方法で得られたアルミナコロイド含有水溶液
JP5282735B2 (ja) 可視光応答型酸化チタン系微粒子分散液およびその製造方法
JP6916021B2 (ja) 炭化水素油の水素化脱硫触媒及び水素化脱硫触媒の製造方法
Saikia et al. Enhanced catalytic activity of supported gold catalysts for oxidation of noxious environmental pollutant CO
KR20070092627A (ko) 광촉매 분산체
WO2022018980A1 (fr) Dispersion de tantalate et composé de tantalate
JP4369165B2 (ja) チタンを含有した担体、その製造方法、炭化水素油の水素化処理触媒及びそれを用いた水素化処理方法
JP4002497B2 (ja) 金属酸化物ゾル及びその製造方法
JP2003080067A (ja) 触媒担体用酸化チタン及びアンモニア脱硝触媒の製造方法
JP4156282B2 (ja) 水溶性チタン化合物及びその製造方法
CN114604881B (zh) 一种可控羟基含量的羟基纳米氧化铝的制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ 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 US 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 ZM 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 TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002551471

Country of ref document: JP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase