CN1169336A - Refined catalyst made by distillate added with hydrogen and preparation thereof - Google Patents
Refined catalyst made by distillate added with hydrogen and preparation thereof Download PDFInfo
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Abstract
The refined catalyst comprises (weight) 1-5% of nickel oxide, 12-355 of tungsten oxide, 1-9% of fluorine and the rest of aluminium oxide. Said aluminum oxide comprises one or more of microporous aluminiumand oxide and one or more of macroporous aluminium oxide the two ratio is 75:25-50:50 (weight ratio), in which the porosities whose porosity-diameter is smaller than 80 angstrom account for over 95% of the total microporous aluminium oxide volume, and the porosities whose diameter is of 60-600 angstrom account for over 70% of the total macroporous aluminium oxide. Said catalyst is specially suitable to the hydrogen refining in 80-550 degree C boiling range/of faulty distillate high sulfur-content.
Description
The invention relates to a kind of catalyst for hydrorefining distillate oil and preparation thereof, specifically about a kind of catalyst for hydrorefining distillate oil and preparation thereof of nickeliferous and tungsten.
In recent years, crude oil poor qualityization tendency is obvious day by day in the world wide, and sulphur nitrogen and arene content increase day by day in the oil product, and obviously, more and more the contradiction between Yan Ge environmental requirement and this reality is more sharp-pointed; As everyone knows, hydrogenation is to improve oil quality one of the most effective process means, hydrogenation catalyst then is the most important and crucial technology of this technology, therefore, many major companies all are devoted to the improvement to existing Hydrobon catalyst, do not disconnect and send the better Hydrobon catalyst of performance.
Catalyst for hydrorefining distillate oil generally is made up of with carrier and auxiliary agent with certain acid function metal with hydrogenating function or metal oxide, metal component commonly used is cobalt-molybdenum or nickel-molybdenum, and use nickel-tungsten more and more recently as the Hydrobon catalyst of active component, its developing direction is further to reduce the content of metal in the catalyst, and the character of change catalyst carrier makes it to be more suitable for the hydrofinishing of low grade oils.
US 3,779, dry and the roasting with alumina sol in 903, make the carrier that pore volume is 0.15～0.45ml/g, also drying, roasting make the catalyst that contains nickel oxide 10～18 heavy %, tungsten oxide 25～40 heavy % and 1～9 heavy % fluorine to flood tungsten, nickel then, this catalyst is because tenor, particularly nickel too high levels cause the catalyst cost too high.
US 4,330,395 to disclose a kind of be raw material with tungsten compound and aluminium compound, by evaporate to dryness, roasting, flood with nickel compound, vulcanize and fluoridize with sulphur compound and fluorine compounds then, prepare a kind of catalyst for hydrorefining distillate oil, this catalyst has the too high shortcoming of tenor equally, and its preparation method is more complicated also.
CN 85,104, the high single diaspore of the method preparation of 438 B employing aluminum alkoxide or alkyl aluminum hydrolysis is as the precursor of catalyst carrier, prepare a kind of Hydrobon catalyst that contains nickel oxide 1～5 heavy %, tungsten oxide 12～35 heavy %, fluorine 1～9 heavy %, this catalyst has lower tenor and higher hydrogenation activity, but, cause the catalyst cost higher because the precursor price of catalyst carrier is more expensive.
CN 1 in addition, 105,053 discloses a kind of hydrorefined catalyst of heavy distillate that is applicable to, the nickel oxide 1～5 that consists of of this catalyst weighs %, tungsten oxide 15～38 heavy %, fluorine 1～9 heavy %, its carrier is a kind ofly at high temperature to handle the modified aluminas that obtains with air and water vapour, this modified aluminas pore distribution concentration is in 60～200 dust scopes, because the step that has adopted air and water vapour at high temperature to handle, this method obviously exists complicated process of preparation, the higher shortcoming of energy consumption.
The objective of the invention is on the basis of above-mentioned prior art, provide a kind of cost lower and active higher catalyst for hydrorefining distillate oil.
Another object of the present invention provides the preparation method of this Hydrobon catalyst.
Other purpose of the present invention can be learnt from the specification that comprises embodiment.
Catalyst provided by the invention has following composition: nickel oxide 1～5 heavy %, tungsten oxide 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminium oxide, this aluminium oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, to be bore dia account for the aluminium oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminium oxide of total pore volume more than 70%, and described pore size distribution adopts B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
This Preparation of catalysts method provided by the invention comprises the moulding of aluminium oxide precursor, use the precursor aqueous solution dipping of fluorinated water solution and nickel-tungsten after the roasting successively, each dipping back drying and roasting, the described aluminium oxide precursor pore volume that to be bore dia account for the precursor of the little porous aluminum oxide of total pore volume more than 95% and bore dia 60～600 dust holes less than the pore volume in 80 dust holes accounts for the mixture of the precursor of the macroporous aluminium oxide of total pore volume more than 70%, and it is 75: 25～50: 50 that the ratio of medium and small porous aluminum oxide precursor of mixture and macroporous aluminium oxide precursor should make the weight ratio of medium and small porous aluminum oxide of the catalyst carrier that finally obtains and macroporous aluminium oxide.
According to catalyst provided by the invention, it consists of: nickel oxide 1～5 heavy %, and tungsten oxide 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminium oxide, this aluminium oxide is composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides.Generally, this aluminium oxide is to be composited by a kind of little porous aluminum oxide and a kind of macroporous aluminium oxide.The compositely proportional of above-mentioned two kinds of aluminium oxide is that the weight of the feedstock oil processed according to this catalyst is adjusted.When being lightweight fraction oil, can strengthen raw material the consumption of little porous aluminum oxide; When being heavy distillate, then should strengthen raw material the consumption of macroporous aluminium oxide.When being used for 80～550 ℃ petroleum cuts hydrofinishing, the weight ratio of little porous aluminum oxide and macroporous aluminium oxide should be 75～25～50: 50, at this moment, the alumina support after compound should have following pore size distribution: the pore volume in diameter 40～100 dust holes accounts for more than 75% of total pore volume.Here to be bore dia account for the aluminium oxide of cumulative volume more than 95% less than the pore volume in 80 dust holes to said little porous aluminum oxide; Macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminium oxide of total pore volume more than 70%.
In catalyst provided by the invention, its alumina catalyst support also has the specific surface and the pore volume of the routine of general hydrogenation catalyst except that having above-mentioned pore size distribution, preferred 200 meters of its specific surface
2More than/the gram, more preferred 220 meters
2/ gram, preferred 0.3 milliliter of pore volume/more than the gram, more preferred 0.4 milliliter/more than the gram.
According to above-mentioned Preparation of catalysts method provided by the invention, its preparation process is as follows:
1. the preparation of carrier: the precursor that the pore volume that bore dia is accounted for the precursor of the little porous aluminum oxide of total pore volume more than 95% and bore dia 60～600 dust holes less than the pore volume in 80 dust holes accounts for the macroporous aluminium oxide of total pore volume more than 70% mixes according to predetermined ratio, after the Hydrobon catalyst forming method moulding routinely in 550～650 ℃ of roastings 3～5 hours;
2. the dipping of fluorine: with the above-mentioned alumina support of fluorinated water solution impregnation, after 100～130 ℃ of oven dry in 400～600 ℃ of roastings 3～5 hours;
3. the dipping of nickel-tungsten: flood above-mentioned fluoro-containing alumina carrier with nickeliferous and aqueous solution tungsten, after 100～130 ℃ of oven dry in 40～600 ℃ of roastings 3～5 hours.
Wherein preferably a diaspore content is greater than the hydrated alumina of 60 heavy % for the precursor of said little porous aluminum oxide, and it can make with sodium metaaluminate-carbon dioxide process; Preferably a diaspore content is greater than the hydrated alumina of 50 heavy % for the precursor of macroporous aluminium oxide, and it can make with sodium metaaluminate-aluminum sulfate method.
Wherein said conventional forming method comprises methods such as compressing tablet, balling-up or extrusion, preferably adopts the method for extruded moulding.
Wherein said fluorinated water solution refers to fluorine-containing inorganic compound aqueous solution, as the ammonium fluoride and/or the hydrofluoric aqueous solution.
The mixed aqueous solution that the aqueous solution of wherein said tungstenic and nickel is generally made by ammonium metatungstate, ammonium tungstate, ethyl ammonium metatungstate or metatungstic acid nickel and nickel nitrate or nickel acetate.
Owing to adopted alumina support with special pore size distribution, catalyst provided by the invention has the catalytic activity higher than prior art, for example, the catalyst that the preparing carriers that is composited by 70: 30 weight ratio with little porous aluminum oxide and macroporous aluminium oxide goes out, its desulfurization, denitrogenation and aromatic saturated hydrogenation activity all are higher than the catalyst disclosed in CN 85104438 B, and when catalyst provided by the invention is used for the hydrofinishing of high-sulfur inferior distillate oil, still has advantages of high catalytic activity.
The most outstanding technical characterictic of the present invention has been to utilize the aluminium oxide of different pore size distributions to prepare the catalyst carrier that is suitable as fraction oil hydrogenation refining, though macroporous aluminium oxide helps the diffusion of more macromolecular reactant and product, be suitable as the carrier of catalyst for hydrorefining distillate oil, yet, as everyone knows, hole too conference produces adverse influence to the intensity of catalyst carrier, little porous aluminum oxide is unfavorable for the diffusion of reactant and product, but just in time remedied the shortcoming that above-mentioned macroporous aluminium oxide exists, the present invention has made full use of the character of different pore size distribution aluminium oxide, it is combined dexterously, the lower advantage of catalyst metal content that has not only kept CN 85104438 B to disclose, and can utilize the content of different pore size distribution aluminium oxide in carrier, adjust the character of catalyst carrier neatly, make it to be suitable for the unifining process of various distillates.
In addition, because of the price of the hydrated alumina of sodium metaaluminate-carbon dioxide process preparation only be 1/9th of the hydrated alumina for preparing of aluminum alkoxide or alkyl aluminum hydrolysis method or sodium metaaluminate-aluminum sulfate method, thereby the cost of catalyst carrier provided by the invention is reduced significantly, for example, the cost that respectively accounts for the catalyst carrier of preparing after 50 ratio composite molding and the roasting in two kinds of hydrated aluminas is 61% of the catalyst carrier that discloses of CN 85104438B.
Catalyst provided by the invention is specially adapted to the hydrofinishing that boiling range is 80～550 ℃ a fraction oil of petroleum, catalyst provided by the invention and hydrocracking catalyst are used the hydro-upgrading that then can be used for heavy distillate, particularly the MHUG process.
When being used for fraction oil hydrogenation refining, can use by catalyst provided by the invention conventional hydrofining technology condition, as 200～500 ℃ of reaction temperatures, and preferred 300～400 ℃, reaction pressure 2～24 MPas, preferred 3～15 MPas, liquid hourly space velocity (LHSV) 0.1～30 hour
-1, preferred 0.2～10 hour
-1, hydrogen to oil volume ratio 50～5000, preferred 200～1000.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Comparative Examples 1
The method that provides by CN 85104438 B prepares comparative catalyst's carrier.
Take by weighing hydrated alumina (the trade name SB of aluminum alkoxide Hydrolyze method preparation, Germany Condea company product, wherein a water aluminium content 85 weighs %) 200 grams (in butt weight), add extrusion aid respectively, adhesive and water are extruded into circumscribed circle diameter and are 1.4 millimeters trilobal cross bar, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours promptly get comparative catalyst's carrier A.Recording its specific surface with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature (down together) is 232m
2/ g, pore volume is 0.47 a milliliter/gram, its pore size distribution is: the volume in bore dia 20～40 dust holes accounts for 7.4% of total pore volume, bore dia be the pore volume in 40～80 dust holes account for total pore volume 84.2%, the pore volume in 80～100 dust holes accounts for 6.8% of total pore volume, bore dia be the pore volume in 100～600 dust holes account for total pore volume 1.6%
Example 1～5
The preparation of catalyst carrier provided by the invention.
Take by weighing precursor (first kind of hydrated alumina of a certain amount of little porous aluminum oxide, the industrial products that sodium metaaluminate-carbon dioxide process makes, name of product is dried boehmite, Shandong Aluminum Plant produces, wherein a diaspore content 80 weighs %, the heavy % of gibbsite content 5, the specific surface and the pore size distribution of the little porous aluminum oxide (B) that forms after 4 hours through 550 ℃ of roastings are listed in the table 1).Other takes by weighing precursor (second kind of hydrated alumina of a certain amount of macroporous aluminium oxide, the industrial products that sodium metaaluminate-the aluminum sulfate method makes, name of product is the Chang Ling dry glue powder, Chang Ling oil plant catalyst plant is produced, one diaspore content, 68 heavy %, the heavy % of gibbsite content 5, the specific surface and the pore size distribution of the macroporous aluminium oxide (C) that forms after 4 hours through 550 ℃ of roastings are listed in the table 1).The butt weight ratio of two kinds of hydrated aluminas by 75: 25～50: 50 mixed, add extrusion aid, adhesive and water, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal cross bar, 120 ℃ of oven dry, respectively 550～650 ℃ of roastings 4 hours, make catalyst carrier D～H, its specific surface and pore size distribution are listed in the table 1.
Table 1
| Example number | ????1 | ????2 | ????3 | ????4 | ????5 | ||
| The aluminium oxide numbering | ????B | ????C | ????D | ????E | ????F | ????G | ????H |
| First and second kinds of hydrated alumina weight ratios (butt) | ????- | ????- | ??75∶25 | ??75∶25 | ??75∶25 | ??70∶30 | ??50∶50 |
| Sintering temperature ℃ | ??550 | ??550 | ??620 | ??550 | ??650 | ??550 | ??550 |
| Roasting time, hour | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 |
| Specific surface, rice 2/ gram | ??236 | ??262 | ???236 | ??248 | ??217 | ??232 | ??228 |
| Pore volume, milliliter/gram | ??0.40 | ??0.63 | ???0.49 | ??0.49 | ??0.49 | ??0.49 | ??0.52 |
| Pore size distribution, dust, % 20～40 40～60 60～80 80～100 100～600 | ??13.0 ??54.1 ??30.6 ??0.8 ??1.5 | ??0.9 ??19.9 ??49.9 ??15.5 ??13.8 | ???5.9 ???24.2 ???60.1 *???9.8 | ??8.2 ??41.7 ??42.2 *??7.8 | ??4.1 ??18.7 ??66.9 *??10.3 | ??5.6 ??23.6 ??60.9 *??9.9 | ??3.4 ??18.1 ??60.1 *??18.4 |
*The pore size distribution of 60～100 dusts
Example 6～16
Preparation of catalysts provided by the invention.
Take by weighing the alumina support D～H of a certain amount of example 1～5 preparation respectively, flooded 1 hour with a certain amount of ammonium fluoride (chemical pure) aqueous solution, 120 ℃ of oven dry, roasting is 4 hours under different temperatures, obtain the fluoro-containing alumina carrier, table 2 has provided each raw material consumption and sintering temperature and time.
Mixed aqueous solution with quantitative ammonium metatungstate (chemical pure) and nickel nitrate (chemical pure) flooded the fluoro-containing alumina carrier 4 hours, 120 ℃ of oven dry, roasting is 4 hours under different temperatures, make catalyst I～S, table 3 has provided each raw material consumption, sintering temperature and time, table 4 item has provided the composition of the catalyst of preparing, wherein NiO, WO
3Content assaying method is referring to " petrochemical industry analytical method " (RIPP test method(s)), and P 360～361, Science Press (1990), and the assay method of fluorine is referring to the P185 that ibidems～187 page.
Comparative Examples 2
The method that provides by CN 85104438 B prepares the comparative catalyst.
Take by weighing the catalyst carrier A of Comparative Examples 1 preparation, prepare catalyst T by example 6～16 described methods, each raw material consumption, sintering temperature and time, the catalyst composition is respectively in table 2～4.
Table 2
| Example number | Used carrier | The dipping of fluorine | Roasting condition | |||
| Numbering | Consumption, gram | NH 4The F consumption, gram | Water consumption, milliliter | Temperature, ℃ | Time, hour | |
| 6789 10 11 12 13 14 15 16 Comparative Examples 2 | ??D ??E ??E ??E ??E ??E ??E ??E ??F ??G ??H ??A | ??50 ??200 ??50 ??50 ??50 ??50 ??50 ??50 ??50 ??200 ??200 ??200 | ????6.0 ????22.6 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????12.6 ????6.0 ????22.6 ????22.6 ????30.0 | ????33 ????132 ????33 ????33 ????33 ????33 ????33 ????33 ????33 ????132 ????132 ????120 | ????530 ????530 ????450 ????500 ????530 ????530 ????530 ????530 ????530 ????530 ????530 ????530 | ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 |
Table 3
| Example number | The dipping of nickel-tungsten | Roasting condition | |||
| The nickel nitrate consumption, gram | The ammonium metatungstate consumption, gram | Water consumption, milliliter | Temperature, ℃ | Time, hour | |
| 6789 10 11 12 13 14 15 16 Comparative Examples 2 | ?????6.0 ?????24.2 ?????6.0 ?????6.0 ?????6.0 ?????6.0 ?????11.7 ?????4.3 ?????6.0 ?????24.2 ?????24.2 ?????27.2 | ?????17.5 ?????70.0 ?????17.5 ?????17.5 ?????17.5 ?????17.5 ?????10.8 ?????27.4 ?????17.5 ?????70.0 ?????70.0 ?????80.0 | ????32 ????128 ????32 ????32 ????32 ????32 ????32 ????32 ????32 ????128 ????128 ????120 | ??500 ??500 ??500 ??500 ??420 ??480 ??500 ??500 ??420 ??500 ??500 ??500 | ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????4 |
Table 4
| Example number | The catalyst numbering | Active component content in the catalyst, heavy % | ||
| ????WO 3 | ????NiO | ????F | ||
| 6789 10 11 12 13 14 15 16 Comparative Examples 2 | ????I ????J ????K ????L ????M ????N ????O ????P ????Q ????R ????S ????T | ????22.0 ????21.3 ????22.0 ????22.1 ????22.0 ????21.9 ????14.0 ????30.0 ????21.8 ????22.0 ????22.0 ????24.5 | ????2.3 ????2.3 ????2.3 ????2.3 ????2.3 ????2.3 ????4.8 ????1.5 ????2.3 ????2.3 ????2.3 ????2.5 | ????4.0 ????4.0 ????3.9 ????3.9 ????4.1 ????4.0 ????2.0 ????7.6 ????3.9 ????4.0 ????4.0 ????4.5 |
Example 17～27
Following example illustrates the toluene saturated hydrogenation activity of catalyst provided by the invention.
Hexane solution with 50 heavy % toluene is a raw material, on the small stationary bed reaction device, carry out activity rating, catalyst I～S packs in reactor, catalyst loading amount 1.5 grams (40～60 order), under 300 ℃ of hydrogen atmospheres,, feed reaction raw materials then, 360 ℃ of reaction temperatures with the cyclohexane solution presulfurization of 3 heavy % carbon disulfide 2 hours, reaction pressure 4.1 MPas, weight (hourly) space velocity (WHSV) (WHSV) 3.4 hours
-1, hydrogen to oil volume ratio 400 reacts sampling after 3 hours, product gas-chromatography on-line analysis, and reaction result is listed in the table 5.
Comparative Examples 3
The explanation of this Comparative Examples, the toluene saturated hydrogenation activity of catalyst provided by the invention is better than prior art.
Raw materials used and the method for activity rating is with example 17～27, and just catalyst system therefor is the catalyst T of Comparative Examples 2 preparations, and the results are shown in Table 5 for gained.
By the result of table 5 as can be seen, under identical reaction condition, the toluene saturated hydrogenation activity of catalyst provided by the invention all is higher than comparative catalyst T.
Table 5
| Example number | Catalyst | Toluene conversion, heavy % |
| 17 18 19 20 21 22 23 24 25 26 27 Comparative Examples 3 | ????I ????J ????K ????L ????M ????N ????O ????P ????Q ????R ????S ????T | ?????34.9 ?????35.6 ?????34.7 ?????35.6 ?????38.0 ?????33.5 ?????33.0 ?????36.2 ?????35.3 ?????32.1 ?????33.0 ?????31.0 |
Example 28～29
The following examples illustrate the desulfurization removing nitric activity of catalyst provided by the invention.
The evaluation of catalyst desulfurizing, nitrogen activity is carried out under medium-sized hydrogenation plant, catalyst is J, 100 milliliters of catalyst loading amounts (2～3 millimeters of catalyst length), adopting boiling range is that 186～350 ℃ of catalytic cracking diesel oils are raw material, before the reaction, under 300 ℃ of hydrogen atmospheres, catalyst was carried out presulfurization 3 hours earlier with the virgin kerosene that contains 2 heavy % carbon disulfide, make it change into sulphided state, feed feedstock oil then and carry out hydrogenation reaction, reaction temperature is respectively 330 and 350 ℃, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity (LHSV) (LHSV) 2.0h
-1, hydrogen to oil volume ratio 350, product adopts the legal S of electric weight, the legal N of chemiluminescence, and reaction result is listed in the table 6.
Comparative Examples 4～5
This Comparative Examples illustrates that the desulfurization of catalyst provided by the invention, nitrogen activity are higher than prior art.
Evaluation method and raw material are with example 28～29, and just catalyst system therefor is the catalyst T of Comparative Examples 2 preparations, and reaction result is listed in the table 6.
The presentation of results of table 6, no matter catalyst provided by the invention is that desulfurization or denitrification activity all are higher than the comparative catalyst.
Table 6
| Example number | ????28 | ???29 | Comparative Examples 4 | Comparative Examples 5 | |
| The catalyst numbering | ????J | ???J | ????T | ????T | |
| Reaction temperature, ℃ | ????330 | ???350 | ????330 | ????350 | |
| Nitrogen content ppm | Raw material | ????851 | ???851 | ????851 | ????851 |
| Product | ????204 | ???129 | ????226 | ????167 | |
| Denitrification percent, heavy % | ????76.0 | ???84.8 | ????73.4 | ????80.4 | |
| Sulfur content ppm | Raw material | ????4716 | ???4716 | ????4716 | ????4716 |
| Product | ????280 | ???79 | ????370 | ????185 | |
| Desulfurization degree, heavy % | ????94.1 | ???98.3 | ????92.2 | ????96.1 | |
Example 30～32
Following embodiment illustrates the hydrofinishing performance of catalyst provided by the invention to high-sulfur feedstock oil.
Catalyst and loading amount thereof, experiment reaction unit, the method for pre-sulphuration of catalyst is with example 28～29, be used reaction raw materials be the upright diesel oil (boiling range is 235～366 ℃) that heats up in a steamer in the Saudi Arabia, reaction temperature is 330,340 and 350 ℃, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity (LHSV) (LHSV) 2.0h
-1, hydrogen to oil volume ratio 400, reaction result is listed in the table 7.
Comparative Examples 6～8
The explanation of this Comparative Examples, when catalyst provided by the invention was used for the hydrofinishing of high-sulfur feedstock oil, its catalytic performance also was better than prior art.
Evaluation method and raw material are with example 30～32, and just catalyst system therefor is the catalyst T of Comparative Examples 2 preparations, and reaction result is listed in the table 7.
The presentation of results of table 7, when catalyst provided by the invention is used for sulfur content up to the feedstock oil hydrofinishing of 12784ppm, under each reaction temperature, activity of such catalysts provided by the invention is all apparently higher than comparative catalyst T, this illustrates that catalyst provided by the invention not only is fit to the hydrofinishing of high nitrogen low sulfur content feedstock oil, and the hydrofinishing of suitable high sulfur content inferior feedstock oil, its catalytic activity is better than prior art.
Table 7
| Example number | ????30 | ????31 | ????32 | Comparative Examples 6 | Comparative Examples 7 | Comparative Examples 8 |
| Catalyst | ????J | ????J | ????J | ????T | ????T | ????T |
| Reaction temperature, ℃ | ????330 | ????340 | ????350 | ????330 | ????340 | ????350 |
| Feed sulphur content, ppm | ????12784 | ????12784 | ????12784 | ????12784 | ????12784 | ????12784 |
| The product sulfur content, ppm | ????614 | ????221 | ????59 | ????1084 | ????514 | ????153 |
| Desulfurization degree, heavy % | ????95.2 | ????98.3 | ????99.5 | ????91.5 | ????96.0 | ????98.8 |
Claims (10)
1. fraction oil Hydrobon catalyst, it consists of nickel oxide 1～5 heavy %, tungsten oxide 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminium oxide, it is characterized in that described aluminium oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, to be bore dia account for the aluminium oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminium oxide of total pore volume more than 70%, and described pore size distribution adopts B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
2. catalyst according to claim 1 is characterized in that described aluminium oxide is composited by a kind of little porous aluminum oxide and a kind of macroporous aluminium oxide.
3. catalyst according to claim 1 and 2, the precursor that it is characterized in that described little porous aluminum oxide are the hydrated alumina of a diaspore content greater than 60 heavy %, and the precursor of macroporous aluminium oxide is the hydrated alumina of a diaspore content greater than 50 heavy %.
4. catalyst according to claim 1 and 2 is characterized in that the pore volume that described aluminium oxide median pore diameter is 40～100 dusts accounts for more than 75% of total pore volume.
5. catalyst according to claim 1 and 2, the specific surface that it is characterized in that described aluminium oxide is 220 meters
2More than/the gram, pore volume be 0.4 milliliter/gram more than.
6. claim 1 Preparation of catalysts method comprises the moulding of aluminium oxide precursor, use the precursor aqueous solution dipping of fluorinated water solution and nickel-tungsten after the roasting successively, each dipping back drying and roasting, it is characterized in that the described aluminium oxide precursor pore volume that to be bore dia account for the precursor of the little porous aluminum oxide of total pore volume more than 95% and bore dia 60～600 dust holes less than the pore volume in 80 dust holes accounts for the mixture of the precursor of the macroporous aluminium oxide of total pore volume more than 70%, it is 75: 25～50: 50 that the ratio of medium and small porous aluminum oxide precursor of mixture and macroporous aluminium oxide precursor should make the weight ratio of medium and small porous aluminum oxide of the catalyst carrier that finally obtains and macroporous aluminium oxide.
7. preparation method according to claim 6, the precursor that it is characterized in that described little porous aluminum oxide are the hydrated alumina that a diaspore content is worked energetically 60 heavy %.
8. preparation method according to claim 7 is characterized in that described hydrated alumina is the hydrated alumina of sodium metaaluminate-carbon dioxide process preparation.
9. preparation method according to claim 6, the precursor that it is characterized in that described macroporous aluminium oxide are the hydrated alumina of a diaspore content greater than 50 heavy %.
10. preparation method according to claim 9 is characterized in that described hydrated alumina is the hydrated alumina of sodium metaaluminate-aluminum sulfate method preparation.
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| CN97112397A CN1057021C (en) | 1996-06-28 | 1997-06-18 | Refined catalyst made by distillate added with hydrogen and preparation thereof |
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| CN96106724 | 1996-06-28 | ||
| CN96106724.1 | 1996-06-28 | ||
| CN97112397A CN1057021C (en) | 1996-06-28 | 1997-06-18 | Refined catalyst made by distillate added with hydrogen and preparation thereof |
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| CN1057021C CN1057021C (en) | 2000-10-04 |
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| CN (1) | CN1057021C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055951C (en) * | 1997-12-23 | 2000-08-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| US6518219B1 (en) | 1999-10-14 | 2003-02-11 | China Petrochemical Corporation | Catalyst for hydrorefining fraction oils, its carrier and preparation |
| CN1311905C (en) * | 2004-04-29 | 2007-04-25 | 中国石油化工股份有限公司 | Hydrodemetalization catalyst for residual oil and process for preparing same |
| CN100496738C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
| CN102274732A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274731A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274730A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102453546A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Deep processing method for shale oil |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN104001539A (en) * | 2014-05-14 | 2014-08-27 | 北京石油化工学院 | Coal tar hydrocracking pretreatment catalyst and preparation method thereof |
| US9657236B2 (en) | 2012-03-31 | 2017-05-23 | China Petroleum & Chemical Corporation | Process for hydrotreating heavy raw oils |
| WO2020192724A1 (en) * | 2019-03-28 | 2020-10-01 | 中国石油化工股份有限公司 | Catalytic-cracking catalyst and method for preparation thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN85104438B (en) * | 1985-06-13 | 1986-08-06 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst for hydrorefining distillate oil |
| GB2258279B (en) * | 1991-07-29 | 1995-01-18 | Jong Oh Ra | Automatic transmission |
| CN1036791C (en) * | 1994-01-04 | 1997-12-24 | 中国石油化工总公司 | Fine catalyst produced by fraction oil hydrogenation |
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1997
- 1997-06-18 CN CN97112397A patent/CN1057021C/en not_active Expired - Lifetime
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055951C (en) * | 1997-12-23 | 2000-08-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| US6518219B1 (en) | 1999-10-14 | 2003-02-11 | China Petrochemical Corporation | Catalyst for hydrorefining fraction oils, its carrier and preparation |
| CN1311905C (en) * | 2004-04-29 | 2007-04-25 | 中国石油化工股份有限公司 | Hydrodemetalization catalyst for residual oil and process for preparing same |
| CN100496738C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
| CN102274732A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274731A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274730A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274732B (en) * | 2010-06-10 | 2013-03-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274730B (en) * | 2010-06-10 | 2013-03-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274731B (en) * | 2010-06-10 | 2013-06-05 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102453546B (en) * | 2010-10-25 | 2015-03-18 | 中国石油化工股份有限公司 | Deep processing method for shale oil |
| CN102453546A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Deep processing method for shale oil |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN102533329B (en) * | 2010-12-31 | 2014-05-28 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| US9657236B2 (en) | 2012-03-31 | 2017-05-23 | China Petroleum & Chemical Corporation | Process for hydrotreating heavy raw oils |
| CN104001539A (en) * | 2014-05-14 | 2014-08-27 | 北京石油化工学院 | Coal tar hydrocracking pretreatment catalyst and preparation method thereof |
| WO2020192724A1 (en) * | 2019-03-28 | 2020-10-01 | 中国石油化工股份有限公司 | Catalytic-cracking catalyst and method for preparation thereof |
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| CN1057021C (en) | 2000-10-04 |
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