CN104927912A - Hydrotreatment method of hydrocarbon oil raw material with high content of metals - Google Patents
Hydrotreatment method of hydrocarbon oil raw material with high content of metals Download PDFInfo
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Abstract
A hydrotreatment method of hydrocarbon oil raw material with high content of metals is as follows: under the condition of hydrotreating reactions, raw oil sequentially contacts with a catalyst composition comprising a hydrotreatment protection catalyst I, a hydrotreatment catalyst II and a hydrotreatment catalyst III, wherein the hydrotreatment protection catalyst I contains a carrier and hydrogenation active metal components loaded on the carrier, the carrier contains alumina and at least one aid selected from boron, silicon and fluorine aids, and is characterized by mercury intrusion method, the pore volume of the alumina carrier is 0.5-1 ml/g, the specific surface area is 30-150m<2>/g, the most probable pore size is 80-300 nm, the carrier is in bimodal pore size distribution in the range of the diameter of 12-15nm and the diameter of 100-200nm, the pore volume of pores with the diameter of 12-15nm is 10-22% of the total pore volume, and the pore volume of pores with the diameter of 100-200nm is 40-70% of the total pore volume. The method disclosed in the invention has a better inferior raw oil hydrotreatment performance compared with the prior art.
Description
Technical field
The present invention relates to the high hydrocarbon oil crude material hydroprocessing process of a kind of metal content.
Background technology
Along with the continuous aggravation of crude oil heaviness trend and social development are to the continuous increase of light-end products demand, the secondary processing of raw material that poor heavy raw material oil produces light-end products or high-quality by hydroprocessing technique is widely adopted.In order to improve secondary processing as the product slates of catalytic cracking process and operating process, require that hydroprocessed product has the foreign matter content of lower metal, sulphur, nitrogen and carbon residue, and at present along with the aggravation of raw material in poor quality trend, in raw material, metal impurities content constantly increases, and requires that hydroprocessing processes needs to have better impurity removal ability and reaction stability like this.Improve impurity removal ability to be realized by the severity improving hydrotreatment reaction, but also can cause the shortening in catalyst runs life-span like this.Therefore new catalyzer and processing and treating method is adopted to be the optimal selections of production high-quality secondary processing of raw material.
Summary of the invention
The technical problem to be solved in the present invention is for prior art demand, provide a kind of newly, the hydroprocessing process for high metal inferior heavy oil with higher impurity removal ability and reaction stability.
The present invention relates to following content:
1, the hydrocarbon oil crude material hydroprocessing process that a kind of metal content is high, comprise at hydrotreating reaction conditions, by heavy raw oil successively with comprise hydrotreatment guard catalyst I, hydrotreating catalyst II contacts with the catalyst combination of hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreatment guard catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, and the content of hydrotreating catalyst III is 10-60%; Wherein, described hydrotreatment guard catalyst I contains carrier and load hydrogenation active metals component on this carrier; wherein; described carrier contains aluminum oxide and at least one is selected from boron, silicon and fluorine auxiliary agent; characterize with mercury penetration method; the pore volume of described carrier is 0.5-1 ml/g, and specific surface area is 30-150 rice
2/ gram, most probable pore size is 80-300nm, described carrier be 12-15nm and diameter is 100-200nm at diameter is bimodal pore distribution, and described diameter is the 10-22% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 40-70% that the pore volume in 100-200nm hole accounts for total pore volume.
2, the method according to 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreatment guard catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The pore volume of the described shaping carrier in described hydrotreatment guard catalyst I is 0.5-0.8 ml/g, and specific surface area is 50-130 rice
2/ gram, most probable pore size is 80-280nm, and wherein, diameter is the 10-20% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 45-70% that the pore volume in 100-200nm hole accounts for total pore volume.
3, the method according to 1 or 2, is characterized in that, described hydrotreatment guard catalyst I, with the content of the described auxiliary agent boron of oxide basis, silicon for 0.1-8 % by weight, in the Oil repellent of element for 0.1-8 % by weight.
4, the method according to 3, is characterized in that, with the content of the described auxiliary agent boron of oxide basis, silicon for 1-6 % by weight, in the Oil repellent of element for 1-6 % by weight.
5. the method according to 4, is characterized in that, with the content of the described auxiliary agent boron of oxide basis, silicon for 1-4 % by weight, in the Oil repellent of element for 1-4 % by weight.
6, the method according to 1 or 2, it is characterized in that, hydrogenation active metals component in described catalyzer I is selected from the metal component of at least one the VIIIth race and at least one group VIB, with oxide basis and with described catalyzer for benchmark, the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 8 % by weight, and the content of metal component of group VIB is for being greater than 0 to being less than or equal to 10 % by weight.
7, the method according to 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, described metal component of group VIB is selected from molybdenum and/or tungsten, with oxide basis and with described catalyzer for benchmark, the content of described metal component of group VIII is 0.2 ~ 4 % by weight, and the content of metal component of group VIB is 0.5 ~ 8 % by weight.
8, the method according to 1, it is characterized in that, described catalyst II contains carrier, metal component molybdenum, cobalt and nickel, be benchmark with oxide basis and with catalyst II, the content of described molybdenum is 5 ~ 20 % by weight, the content sum of cobalt and nickel is 1 ~ 6 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2 ~ 4.
9, the method according to 8, is characterized in that, is benchmark with oxide basis and with catalyst II, and in described catalyst II, the content of molybdenum is 8 ~ 15 % by weight, and the content sum of cobalt and nickel is 1.5 ~ 4 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2.2 ~ 3.2.
10, the method according to 1, it is characterized in that, described catalyzer III is containing the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
11, the method according to 10, is characterized in that, the support selected from alumina in described catalyzer III.
12, the method according to 11, is characterized in that, the pore volume of described aluminum oxide is not less than 0.35 ml/g, and bore dia is that the pore volume in 40 ~ 100 dust holes accounts for more than 80% of total pore volume.
13, the method according to 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h
-1, hydrogen to oil volume ratio is 600-1500.
14, the method according to 13, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h
-1, hydrogen to oil volume ratio is 800-1100.
The carrier of catalyst I described in the present invention, characterize with mercury penetration method, its pore volume is 0.5-1 ml/g, and specific surface area is 30-150 rice
2/ gram, wherein, diameter is the 10-22% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 40-70% that the pore volume in 100-200nm hole accounts for total pore volume; The pore volume of preferred described shaping carrier is 0.5-0.8 ml/g, and specific surface area is 50-130 rice
2/ gram, wherein, diameter is the 10-20% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 45-70% that the pore volume in 100-200nm hole accounts for total pore volume.
Take carrier as benchmark, in described carrier, the content of auxiliary agent is 0.1-8 % by weight, is preferably 1-6 % by weight, more preferably 1-4 % by weight.Wherein, boron and silicon are with oxide basis, and fluorine is in element.
Hydrogenation active metals component in described catalyst I and content thereof are usually the conventional hydrogenation active metals component of hydrogenation protecting catalyst and content, such as, are selected from least one group VIII non-noble metal components and at least one group vib metal component.The metal component of preferred group VIII is nickel and/or cobalt, the metal component of preferred group vib is molybdenum and/or tungsten, with oxide basis and with described catalyzer for benchmark, the content of described group VIII metal is for being greater than 0 to being less than or equal to 8 % by weight, be preferably 0.2 ~ 4 % by weight, the content of described group vib metal component, for being greater than 0 to being less than or equal to 10 % by weight, is preferably 0.5 ~ 8 % by weight.
The preparation method of carrier described in hydrogenation protecting catalyst I of the present invention, comprise a kind of hydrated aluminum oxide being mixed with a kind of Alpha-alumina and introducing in the mixture and contain at least one and be selected from boron, the compound of silicon and fluorine auxiliary agent, shaping, dry also roasting, maturing temperature is 750-1000 DEG C, be preferably 800-950 DEG C, roasting time is 1-10 hour, be preferably 2-8 hour, wherein, in the ratio of mixture of the hydrated aluminum oxide of butt and Alpha-alumina for 20-75:25-80(wherein, 20-75 refers to that the hydrated aluminum oxide (in butt) of every hundred parts is with the mixture of Alpha-alumina, the value of hydrated aluminum oxide number changes between 20-75, 25-80 refers to that the hydrated aluminum oxide (in butt) of every hundred parts is with the mixture of Alpha-alumina, the value of Alpha-alumina number changes between 25-80), be preferably 30-70:30-70.The pore volume of described hydrated aluminum oxide is 0.9-1.4 ml/g, and be preferably 0.95-1.3 ml/g, specific surface is 100-350 rice
2/ gram be preferably 120-300 rice
2/ gram, most probable bore dia is 8-30nm, is preferably 10-25nm.
In described hydrated aluminum oxide and Alpha-alumina mixture, introduce the method being selected from boron, silicon and fluorine auxiliary compound containing at least one is ordinary method, such as, can be directly the compound containing described adjuvant component of aequum is mixed in aforesaid hydrated aluminum oxide and Alpha-alumina mixing process.
Concrete prepare in the embodiment of carrier at one, in described hydrated aluminum oxide and Alpha-alumina mixture, introduce the method being selected from boron, silicon and fluorine auxiliary compound containing at least one is be mixed with the aqueous solution by being selected from boron, silicon and fluorine auxiliary compound containing at least one, this aqueous solution is mixed into while described hydrated aluminum oxide mixes with Alpha-alumina or again this aqueous solution is mixed into after described hydrated aluminum oxide mixes with Alpha-alumina, aftershaping, dry and roasting.Compound containing described auxiliary agent is one or more in their water-soluble cpdss.Such as, containing one or more in the water-soluble inorganic salt of described auxiliary agent.
Described Alpha-alumina can be commercially available commodity (commodity alpha-aluminium oxide powder), also can be obtained through high-temperature roasting by hydrated aluminum oxide (alumina hydrate powder).Under being enough to that hydrated aluminum oxide roasting phase transformation is converted into the condition of Alpha-alumina, this process can adopt arbitrary existing method to realize, and does not limit this present invention.
It is 0.9-1.4 ml/g that described hydrated aluminum oxide is selected from arbitrary pore volume, and be preferably 0.95-1.3 ml/g, specific surface is 100-350 rice
2/ gram, be preferably 120-300 rice
2/ gram, can and bore dia 8-30nm, be preferably the hydrated aluminum oxide of 10-25nm; Be preferably the hydrated aluminum oxide containing pseudo-boehmite.Here, the pore volume of described hydrated aluminum oxide, specific surface area and can and aperture, be that described hydrated aluminum oxide after 4 hours in 600 DEG C of roastings, is characterized by BET nitrogen absorption under low temperature and obtains.
Described hydrated aluminum oxide adopts ordinary method with mixing of Alpha-alumina, and meets in the ratio of mixture of the hydrated aluminum oxide of butt and Alpha-alumina for 20-75:25-80, preferably 30-70:30-70.
Described carrier requires depending on different the forming composition that can be made into various easy handling, such as spherical, cellular, nest like, tablet or bar shaped (trifolium, butterfly, cylindrical etc.).Shapingly can to carry out according to a conventional method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or tackiness agent, containing or not containing expanding agent, then extrusion moulding, carry out drying also roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, PVOH, described peptizing agent can be mineral acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and tensio-active agent.Synthetic cellulose is wherein preferably one or more in Walocel MT 20.000PV, methylcellulose gum, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the vinylcarbinol multipolymer that tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
Described method that is shaping, dry and roasting is ordinary method.Wherein, it is 750-1000 DEG C that the condition optimization of roasting comprises maturing temperature, and roasting time is 1-10 hour, and it is 800-950 DEG C that the condition of preferably roasting further comprises maturing temperature, and roasting time is 2-8 hour.
The preparation method of described hydrogenation protecting catalyst I, comprises the step introducing hydrogenation active metals component on described carrier, and hydrogenation active metals component is wherein selected from least one group VIII base metal and the combination being selected from least one group vib metal.The metal component of preferred group vib is molybdenum and/or tungsten, with oxide basis and with described catalyzer for benchmark, the introduction volume of described group vib metal component makes the content of group vib metal component in final catalyzer for being greater than 0 to being less than or equal to 10 % by weight, be preferably 0.5 ~ 8 % by weight, the introduction volume of described group VIII metal component makes the content of group VIII metal component in final catalyzer for being greater than 0 to being less than or equal to 8 % by weight, is preferably 0.2 ~ 4 % by weight.
What on described carrier, introduce hydrogenation active metals component can be any means that those skilled in the art inform, such as, by carrier described in the solution impregnation with the compound containing described hydrogenation active metals component, the step of drying, roasting or not roasting can be carried out afterwards.
Wherein, the described compound containing group vib metal be selected from they soluble compound in one or more.Such as, the compound containing molybdenum can be one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; Tungstenic compound is selected from one or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.
The described compound containing group VIII metal be selected from they soluble compound in one or more.Such as, the compound containing cobalt can be one or more in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride, is preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous dihydroxycarbonate; Nickel compound containing can be one or more in nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride, is preferably nickelous nitrate, basic nickel carbonate.
According to the present invention, all kinds of SOLVENTS that this area can be adopted to commonly use prepares the solution of the compound containing described activeconstituents, as long as described compound can be dissolved in described solvent, forms the solution of stable homogeneous.Such as: described solvent can for water or carbonatoms be 1 ~ 5 alcohol (as: ethanol), be preferably water and/or ethanol, be more preferably water.
The method of described dipping can be the conventional various dipping methods in this area, such as, can be the saturated pickling process in hole.The present invention was not particularly limited for the time of described dipping and the number of times of dipping, as long as can guarantee that the amount with the activeconstituents of katalysis on the catalyzer that finally obtains meets concrete service requirements.Usually, the time of described dipping can be 0.5 ~ 12 hour.
The present invention, the carrier for compound load being had described hydrogenation active metals component carries out dry method and condition is not particularly limited.Usually, the temperature of described drying can be 80 ~ 350 DEG C, is preferably 100 ~ 300 DEG C; The time of described drying can be 0.5 ~ 24 hour, is preferably 1 ~ 12 hour.
When catalyzer after drying needs to carry out roasting, the present invention is not particularly limited described roasting method and condition, can be ordinary method and the condition of this area.Usually, the temperature of described roasting can be 350 ~ 650 DEG C, is preferably 400 ~ 500 DEG C; The time of described roasting can be 0.2 ~ 12 hour, is preferably 1 ~ 10 hour.Described roasting can be carried out in oxygen-containing atmosphere, also can carry out in an inert atmosphere.
In the present invention, the effect of described catalyst II is to remove macromole species and the partial vulcanization things such as organo-metallic impurity, bituminous matter and the colloid in raw material further.
According to method provided by the invention, wherein, meeting under the prerequisite that the present invention requires described hydrotreating catalyst II, described hydrotreating catalyst II can be commercially available commodity, and arbitrary prior art also can be adopted to prepare.Such as, disclosed in 20110276687.3 and 201110039566.1, Catalysts and its preparation method is suitable for the present invention completely.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.
In the present invention, the effect of described catalyzer III is the macromolecular cpds such as saturated polycyclic aromatic hydrocarbons, the wherein more difficult impurity such as sulphur, nitrogen removed is removed further, removes the carbon residue in stock oil simultaneously, improves product property.Be enough under the prerequisite realizing above-mentioned functions, the present invention does not have other to limit to described catalyzer III, and namely catalyzer III can be selected from the catalyzer such as hydrofining, hydrotreatment that arbitrary prior art provides.They can be commercially available commodity or adopt any existing method preparation.
Usually, this type of catalyzer is usually containing heat-resistant inorganic oxide carrier, hydrogenation active metals component.Such as, described catalyzer III is containing the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, and the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
Such as, a kind of Hydrobon catalyst disclosed in ZL97112397, it consists of the heavy % of nickel oxide 1 ~ 5, the heavy % of Tungsten oxide 99.999 12 ~ 35, the heavy % of fluorine 1 ~ 9, all the other are aluminum oxide, this aluminum oxide be by one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25 ~ 50: 50 weight ratio be composited, wherein little porous aluminum oxide is the aluminum oxide that pore volume that bore dia is less than 80 dust holes accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume in bore dia 60 ~ 600 dust hole accounts for total pore volume more than 70%.
ZL00802168 discloses a kind of Hydrobon catalyst, and this catalyzer contains at least one group VIB metal on this alumina supporter of a kind of alumina supporter and load and/or at least one group VIII metal.The pore volume of described alumina supporter is not less than 0.35 ml/g, and bore dia is that the pore volume in 40 ~ 100 dust holes accounts for more than 80% of total pore volume, and it adopts special method preparation.
ZL200310117323 discloses a kind of Hydrobon catalyst, this catalyzer contains a kind of alumina supporter and load molybdenum on this carrier, nickel and tungsten metal component, be benchmark with oxide basis and with catalyzer, described catalyzer contains the molybdenum of 0.5-10 % by weight, the nickel of 1-10 % by weight, the tungsten of 12-35 % by weight and the carrier of equal amount, the preparation method of described catalyzer comprises and uses the solution of molybdate compound and nickeliferous successively, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina supporter carries out drying after by the solution impregnation of molybdate compound, with nickeliferous, drying and roasting is carried out after the solution impregnation of tungsten compound, drying temperature is 100-300 DEG C, time of drying is 1-12 hour, maturing temperature is 320-500 DEG C, roasting time is 1-10 hour.
These catalyzer all can be used as described catalyzer III for the present invention.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.
According to method provided by the invention, described hydrotreating catalyst I, hydrotreating catalyst II and the hydrotreating catalyst III of comprising can layering fill in same reactor successively, also can be use in the reactor filling in several series connection successively, this present invention is not particularly limited.
According to method provided by the invention, wherein, before the catalyst combination comprising hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III, afterwards or they between any two, any other catalyzer or the filler that contribute to improving described catalyst combination performance can be comprised.Such as, added as fillers such as porcelain ball, active upholders before described Hydrodemetalation catalyst I, to improve stock oil distribution etc. in the reactor.Use etc. about this filler is conventionally known to one of skill in the art, does not repeat here.
According to the ordinary method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, prevulcanized is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this prevulcanized can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metallic sulfide.
According to method provided by the invention, the reaction conditions of described hydrotreatment reaction is the normal condition of heavy oil hydrotreatment, and such as, described reaction conditions comprises: hydrogen dividing potential drop 6-20MPa, and temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1.0h
-1, hydrogen to oil volume ratio is 600-1500, wherein preferred hydrogen dividing potential drop 10-18MPa, and temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h
-1, hydrogen to oil volume ratio is 800-1100.
According to method provided by the invention, be particularly suitable for for higher hydrocarbon oil crude material inferior such as metal content such as processing iron, calcium etc., they can be selected from one or more in crude oil, vacuum residuum, deep drawing wax oil, frivolous asphalt oil, wax tailings, low grade coal tar etc.
Can reach according to the weight of oil after the hydrotreatment that described method obtains: asphalt content is less than 1.2%, and metal Fe+Ca content is 15 below μ g/g, and W metal+V content is 20 below μ g/g, sulphur content less than 0.5%, and carbon residue content is less than 6.0%.
Embodiment
The present invention is described further for the following examples.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Pressure mercury method (RIPP149-90) measures (Yang Cuiding etc., Petrochemical Engineering Analysis method, press of academy of sciences, the 1990, the 421-423 pages) such as the specific surface area of aluminum oxide shaping carrier, pore volume and pore distributions.
BET nitrogen absorption under low temperature method (RIPP151-90) measures specific surface area, the pore volume and pore distribution etc. (Yang Cuiding etc., Petrochemical Engineering Analysis method, press of academy of sciences, the 1990, the 424-426 page) of hydrated aluminum oxide.
Butt measuring method, for getting appropriate amount of sample, in 600 DEG C of roasting temperature 3h, afterwards, calculates the mass percent of sample before sample and roasting after roasting, is the butt of this sample.
Xrf method (RIPP132-90) is adopted to measure constituent content in solid sample (Yang Cuiding etc., Petrochemical Engineering Analysis method, press of academy of sciences, 1990,371-375 page).
Hydrotreatment guard catalyst I in the present invention and preparation method thereof:
Embodiment 1-5 illustrates carrier of preparation catalyst I of the present invention and preparation method thereof.
Embodiment 1
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 200g hydrated aluminum oxide.Pore volume is 1.05 mls/g, and specific surface area is 230 meters
2/ gram, most probable bore dia is 20nm), 70 grams of alpha-aluminium oxide powders (being formed for 6 hours by the hydrated aluminum oxide used in the present embodiment roasting at 1400 DEG C), this mixture and concentration are at room temperature that the ammonia soln 330 milliliters of 4% mixes, after mixing by 9 grams of sesbania powder and 15 grams of borax mixing, kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 2.0mm, afterwards, wet bar through 120 DEG C of dryings after 4 hours in 850 DEG C of roastings 2 hours, obtain carrier ZI1 of the present invention.Measure the specific surface of carrier ZI1, can a few aperture, pore volume, pore distribution, the results are shown in Table 1.
Embodiment 2
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 180g dry glue powder.Pore volume is 1.05 mls/g, and specific surface area is 285 meters
2/ gram, most probable bore dia is 20nm), 120 grams of alpha-aluminium oxide powders (being available commercially from Beijing Shun Chuan Environmental Protection Technology Co., Ltd), 9 grams of sesbania powder and 8 grams of boron oxide mixing, add the aqueous solution 330 milliliters containing 10 grams of Sodium Tetraboratees afterwards, after mixing, in double screw banded extruder, kneading is also extruded with the cylindrical orifice plate of φ 2.0mm, afterwards, wet bar through 120 DEG C of dryings after 4 hours in 850 DEG C of roastings 2 hours, obtain carrier ZI2 of the present invention.Measure the specific surface of carrier ZI2, can a few aperture, pore volume, pore distribution, the results are shown in Table 1.
Embodiment 3
(be available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 68 % by weight to take 150g dry glue powder.Pore volume is 1.08 mls/g, and specific surface area is 188 meters
2/ gram, most probable bore dia is 22nm), 150 grams of alpha-aluminium oxide powders (being available commercially from Beijing Shun Chuan Environmental Protection Technology Co., Ltd), 9 grams of sesbania powder, 9 grams of methylcellulose gum and 20 grams of borax mixing, add the aqueous solution 330 milliliters containing 35 grams of bicarbonate of ammonia afterwards, shaping according to roller forming method after mixing, obtaining particle diameter is 5.5-6.5mm spheroidal particle.Wet bar through 120 DEG C of dryings after 4 hours in 800 DEG C of roastings 2 hours, obtain carrier ZI3 of the present invention.Measure the specific surface of carrier ZI3, can a few aperture, pore volume, pore distribution, the results are shown in Table 1.
Embodiment 4
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 260g dry glue powder.Pore volume is 1.05 mls/g, and specific surface area is 220 meters
2/ gram, most probable bore dia is 20nm), 140 grams of alpha-aluminium oxide powders (with embodiment 1), 9 grams of sesbania powder, 9 grams of methylcellulose gum and 10 grams of magnesium borates mix, add afterwards containing 10 grams of boric acid 5% ammonia soln 300 milliliters, mixing, adds 300 ml waters afterwards, and after mixing, in double screw banded extruder, kneading is also extruded with the cylindrical orifice plate of φ 2.0mm, wet bar through 120 DEG C of dryings after 4 hours in 800 DEG C of roastings 2 hours, obtain carrier ZI4 of the present invention.Measure the specific surface of carrier ZI4, can a few aperture, pore volume, the results are shown in Table 1.
Embodiment 5
(be available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 68 % by weight to take 260g dry glue powder.Pore volume is 1.08 mls/g, and specific surface area is 200 meters
2/ gram, most probable bore dia is 22nm), 140 grams of alpha-aluminium oxide powders (with embodiment 1), 9 grams of sesbania powder, 9 grams of methylcellulose gum mixing, add 300 milliliters, the water containing 10 grams, nitric acid afterwards, mix rear extruded moulding, wet bar through 120 DEG C of dryings after 4 hours in 800 DEG C of roastings 2 hours, obtain carrier ZI5 of the present invention.Measure the specific surface of carrier ZI5, can a few aperture, pore volume, the results are shown in Table 1.
Comparative example 1-4 illustrates preparation reference catalyst carrier and preparation method thereof.
Comparative example 1
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 300 grams of dry glue powders.Pore volume is 0.8 ml/g, and specific surface area is 320 meters
2/ gram, most probable bore dia is 10nm), 9 grams of sesbania powder, add the solution 360 milliliters of mixing mouldings containing 12 grams, nitric acid after mixing, wet bar through 120 DEG C of dryings after 4 hours in 850 DEG C of roastings 2 hours, obtain carrier DZI1.Measure the specific surface of carrier DZI1, can a few aperture, pore volume, the results are shown in Table 1.
Comparative example 2
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 300 grams of dry glue powders.Pore volume is 0.8 ml/g, and specific surface area is 303 meters
2/ gram, most probable bore dia is 11nm), 9 grams of sesbania powder, add the solution 360 milliliters of mixing mouldings containing 12 grams, nitric acid after mixing, wet bar through 120 DEG C of dryings after 4 hours in 950 DEG C of roastings 2 hours, obtain carrier DZI2.Measure the specific surface of carrier DZI2, can a few aperture, pore volume, the results are shown in Table 1.
Comparative example 3
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take dry glue powder.Pore volume is 0.8 ml/g, and specific surface area is 290 meters
2/ gram, most probable bore dia is 11nm) 300 grams, add carbon black powder 24 grams, the mixing of 12 grams, sesbania powder, add containing concentration the aqueous solution 360 milliliters of the phosphoric acid 2.4 grams being 85 % by weight afterwards, kneading 15 minutes, double screw banded extruder is extruded into the butterfly bar of Φ 1.5mm, wet bar through 120 DEG C of dryings after 4 hours in 850 DEG C of roastings 2 hours, obtain carrier DZI3.Measure the specific surface of carrier DZI3, can a few aperture, pore volume, the results are shown in Table 1.
Comparative example 4
(be available commercially from Chang Ling catalyzer branch office, butt is 65 % by weight to take 300 grams of dry glue powders.Pore volume is 0.65 ml/g, and specific surface area is 288 meters
2/ gram, most probable bore dia is 9nm), 9 grams of sesbania powder and 15 grams of boraxs, add the solution 360 milliliters of mixing mouldings containing 12 grams, saltpetre after mixing, wet bar through 120 DEG C of dryings after 4 hours in 950 DEG C of roastings 2 hours, obtain carrier DZI4.Measure the specific surface of carrier DZI4, can a few aperture, pore volume, the results are shown in Table 1.
Table 1
Embodiment 6 ~ 10 is for illustration of catalyst I of the present invention and preparation method thereof.Comparative example 5-6 illustrates reference catalyst and preparation method thereof.
Embodiment 6
Get carrier 100 grams of rear drying and roastings of ZI1 dipping, in saturated leaching mode with containing 1.2g molybdenum oxide (containing MoO
399.9%) and the solution 97 milliliters dipping of 0.7g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst CI1 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Embodiment 7
Get carrier 100 grams of ZI2, in saturated leaching mode with containing 6.42g ammonium molybdate (containing MoO
382%) and the solution 96 milliliters dipping of 4.35g nickelous nitrate (containing NiO51%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst CI2 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Embodiment 8
Get carrier 20 grams of ZI3, in saturated leaching mode with containing 1.2g ammonium molybdate (containing MoO
382%) and the solution 25 milliliters dipping of 2.0g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst CI3 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Embodiment 9
Get carrier 20 grams of ZI4, in saturated leaching mode with containing 0.86g ammonium molybdate (containing MoO
382%) and the solution 13 milliliters dipping of 1.25g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst CI4 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Embodiment 10
Get carrier 20 grams of ZI5, in saturated leaching mode with containing 1.45g ammonium molybdate (containing MoO
382%) and the solution 13 milliliters dipping of 1.30g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst CI5 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Comparative example 5-6 illustrates reference catalyst and preparation method thereof.
Comparative example 5
Get carrier 20 grams of DZI4, in saturated leaching mode with containing 1.2g ammonium molybdate (containing MoO
382%) and the solution 25 milliliters dipping of 2.0g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst DCI1 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Comparative example 6
Get carrier 20 grams of DZI1, in saturated leaching mode with containing 0.86g ammonium molybdate (containing MoO
382%) and the solution 13 milliliters dipping of 1.25g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst DCI2 of the present invention.Wherein, the content of hydrogenation active metals component lists in table 2.
Table 2
Embodiment 11-12 illustrates and is suitable for carrier preparing hydrotreating catalyst II and preparation method thereof.
Embodiment 11
The sesbania powder of pseudo-boehmite dry glue powder RPB110 and 10 gram that 300 grams of Chang Ling catalyzer branch officies produce is mixed, be at room temperature the aqueous nitric acid of 1% by the concentration of this mixture and 360 milliliters, mix, it is after plastic that double screw banded extruder continues kneading, be extruded into the trilobal bar of ф 1.5 millimeters, wet bar after 3 hours, 3 hour obtains carrier Z II 1 in 700 DEG C of roastings through 120 DEG C of dryings.Measure the specific surface of Z II 1, pore volume and pore size distribution, the results are shown in Table 3.
Carrier specific surface, pore volume and pore size distribution adopt B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
Embodiment 12
Pseudo-boehmite dry glue powder by the pseudo-boehmite dry glue powder RPB90 that 300 grams of Chang Ling catalyzer branch officies produce) and 10 grams of sesbania powder mix, add the aqueous nitric acid that 330 ml concns are 1%, mix, it is after plastic that double screw banded extruder continues kneading, be extruded into the butterfly bar of ф 1.1 millimeters, wet bar after 2 hours, 4 hour obtains carrier Z II 2 in 600 DEG C of roastings through 110 DEG C of dryings.Measure the specific surface of Z II 2, pore volume and pore size distribution, result is as shown in table 3.
Table 3
Embodiment 13-16 illustrates by catalyst II of the present invention and preparation method thereof.
Embodiment 13
Carrier Z II 1200 grams prepared by Example 11, with 500 milliliters containing MoO3120 grams per liter, NiO8 grams per liter, the ammonium molybdate of CoO20 grams per liter, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions flood 1 hour, dry 2 hours in 120 DEG C after filtration, 450 DEG C of roastings 4 hours, obtain catalyzer C II 1.With the gross weight of catalyzer for benchmark, adopt the content of the molybdenum oxide in Xray fluorescence spectrometer mensuration catalyzer C II 1, cobalt oxide, nickel oxide, measurement result is as shown in table 4.(all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133-90)
Embodiment 14
Carrier Z II 2200 grams prepared by Example 12, with 220 milliliters containing MoO3172 grams per liter, NiO9 grams per liter, the mixing solutions of the molybdenum oxide of CoO32 grams per liter, basic nickel carbonate, cobaltous dihydroxycarbonate floods 2 hours, dry 2 hours in 120 DEG C, 500 DEG C of roastings 2 hours, obtain catalyzer C II 2.Measure the content of the molybdenum oxide in catalyzer C II 2, cobalt oxide, nickel oxide according to the mode identical with embodiment 3, result is as shown in table 4.
Embodiment 15
Carrier Z II 2200 grams prepared by Example 12, with 200 milliliters containing MoO3122 grams per liter, NiO9 grams per liter, the mixing solutions of the molybdenum oxide of CoO18 grams per liter, basic nickel carbonate, cobaltous dihydroxycarbonate floods 1 hour, dry 2 hours in 120 DEG C, 480 DEG C of roastings 4 hours, obtain catalyzer C II 3.Measure the content of molybdenum oxide, nickel oxide and cobalt oxide in catalyzer C II 3 according to the mode identical with embodiment 3, result is as shown in table 4.
Embodiment 16
Carrier Z II 1200 grams prepared by Example 11,1 hour is flooded with 500 milliliters of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutionss containing CoO12 grams per liter, dry 3 hours in 110 DEG C after filtration, 350 DEG C of roastings 2 hours, with 200 milliliters containing MoO392 grams per liter, molybdenum oxide, the basic nickel carbonate mixing solutions of NiO7 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, 480 DEG C of roastings 4 hours, obtain catalyzer C II 4.Measure the content of molybdenum oxide, nickel oxide and cobalt oxide in catalyzer C II 4 according to the mode identical with embodiment 3, result is as shown in table 4.
Table 4
Embodiment 17-21 illustrates the effect that the invention provides method hydrotreatment residual oil and coal tar mixing raw material.Comparative example 7-8 illustrates the effect of reference method hydrotreatment residual oil raw material.
With Fe+Ca content for 79ppm, Ni+V content be 85ppm, sulphur content is 3.7%, carbon residue be 11.5% coal tar and residual oil mixing low grade oils for raw material, evaluate catalysts on 500 milliliters of fixed-bed reactor.
In oil sample, the content of iron, calcium, nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is U.S. PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90).
In oil sample, sulphur content uses coulometry to measure (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-90).
In oil sample, carbon residue content uses microdetermination (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP149-90).
Hydrotreating catalyst III:
Hydrotreating catalyst III-1, prepares according to the embodiment 6 in patent ZL97112397.7, and it consists of the heavy % of nickel oxide 2.3, the heavy % of Tungsten oxide 99.999 22.0, and the heavy % of fluorine 4, all the other are aluminum oxide.
Hydrotreating catalyst III-2, prepares according to the embodiment 37 in patent ZL00802168.6, and it consists of the heavy % of nickel oxide 2.6, the heavy % of molybdenum oxide 23.6, and the heavy % of fluorine 2.3, all the other are aluminum oxide.
Hydrotreating catalyst III-3, prepares according to the embodiment 3 in patent ZL200310117323.0, and it consists of the heavy % of nickel oxide 2.1, the heavy % of molybdenum oxide 2.5, and the heavy % of Tungsten oxide 99.999 25.4, all the other are aluminum oxide.
Catalyzer usage ratio and processing condition are listed in table 5, and the product property after 1000 hours that operates is listed in table 6.
Comparative example 7
Catalyzer adopts the combination of DCI1, CII1, C III 1, and the volume of each catalyst levels when processing condition is listed in table 5, and operate sampling analysis after 1000 hours, the results are shown in table 6.
Comparative example 8
Catalyzer adopts the combination of DCI2, CII2, C III 2, and the volume of each catalyst levels when processing condition is listed in table 5, and operate sampling analysis after 1000 hours, the results are shown in table 6.
Table 5
Table 6
Can find out, adopt method provided by the invention to operate the foreign matter content such as metal, sulphur, carbon residue of 1000 hours back end hydrogenation treating product, be starkly lower than reference method.
Claims (14)
1. the hydrocarbon oil crude material hydroprocessing process that a metal content is high, comprise at hydrotreating reaction conditions, by heavy raw oil successively with comprise hydrotreatment guard catalyst I, hydrotreating catalyst II contacts with the catalyst combination of hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreatment guard catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, and the content of hydrotreating catalyst III is 10-60%; Wherein, described hydrotreatment guard catalyst I contains carrier and load hydrogenation active metals component on this carrier; wherein; described carrier contains aluminum oxide and at least one is selected from boron, silicon and fluorine auxiliary agent; characterize with mercury penetration method; the pore volume of described carrier is 0.5-1 ml/g, and specific surface area is 30-150 rice
2/ gram, most probable pore size is 80-300nm, described carrier be 12-15nm and diameter is 100-200nm at diameter is bimodal pore distribution, and described diameter is the 10-22% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 40-70% that the pore volume in 100-200nm hole accounts for total pore volume.
2. the method according to 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreatment guard catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The pore volume of the described shaping carrier in described hydrotreatment guard catalyst I is 0.5-0.8 ml/g, and specific surface area is 50-130 rice
2/ gram, most probable pore size is 80-280nm, and wherein, diameter is the 10-20% that the pore volume in 12-15nm hole accounts for total pore volume, and diameter is the 45-70% that the pore volume in 100-200nm hole accounts for total pore volume.
3. the method according to 1 or 2, is characterized in that, described hydrotreatment guard catalyst I, with the content of the described auxiliary agent boron of oxide basis, silicon for 0.1-8 % by weight, in the Oil repellent of element for 0.1-8 % by weight.
4. the method according to 3, is characterized in that, with the content of the described auxiliary agent boron of oxide basis, silicon for 1-6 % by weight, in the Oil repellent of element for 1-6 % by weight.
5. the method according to 4, is characterized in that, with the content of the described auxiliary agent boron of oxide basis, silicon for 1-4 % by weight, in the Oil repellent of element for 1-4 % by weight.
6. the method according to 1 or 2, it is characterized in that, hydrogenation active metals component in described catalyzer I is selected from the metal component of at least one the VIIIth race and at least one group VIB, with oxide basis and with described catalyzer for benchmark, the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 8 % by weight, and the content of metal component of group VIB is for being greater than 0 to being less than or equal to 10 % by weight.
7. the method according to 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, described metal component of group VIB is selected from molybdenum and/or tungsten, with oxide basis and with described catalyzer for benchmark, the content of described metal component of group VIII is 0.2 ~ 4 % by weight, and the content of metal component of group VIB is 0.5 ~ 8 % by weight.
8. the method according to 1, it is characterized in that, described catalyst II contains carrier, metal component molybdenum, cobalt and nickel, be benchmark with oxide basis and with catalyst II, the content of described molybdenum is 5 ~ 20 % by weight, the content sum of cobalt and nickel is 1 ~ 6 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2 ~ 4.
9. the method according to 8, is characterized in that, is benchmark with oxide basis and with catalyst II, and in described catalyst II, the content of molybdenum is 8 ~ 15 % by weight, and the content sum of cobalt and nickel is 1.5 ~ 4 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2.2 ~ 3.2.
10. the method according to 1, it is characterized in that, described catalyzer III is containing the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
11. methods according to 10, is characterized in that, the support selected from alumina in described catalyzer III.
12. the method according to 11, is characterized in that, the pore volume of described aluminum oxide is not less than 0.35 ml/g, and bore dia is that the pore volume in 40 ~ 100 dust holes accounts for more than 80% of total pore volume.
13. the method according to 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h
-1, hydrogen to oil volume ratio is 600-1500.
14. the method according to 13, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h
-1, hydrogen to oil volume ratio is 800-1100.
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| CN114433245A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate oil |
| CN116020497A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Composite carrier, hydrogenation catalyst, and preparation method and application thereof |
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| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| CN103059929A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method for heavy residual oil |
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| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| CN103059929A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method for heavy residual oil |
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| CN114433245A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate oil |
| CN114433245B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate |
| CN116020497A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Composite carrier, hydrogenation catalyst, and preparation method and application thereof |
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