CN102039139B - Hydrocarbon oil hydrogenation depickling catalyst and application thereof - Google Patents
Hydrocarbon oil hydrogenation depickling catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrocarbon oil hydrogenation depickling catalyst and the application thereof. The hydrogenation depickling catalyst comprises carriers and active metals. The carriers comprise alumina and clay material. The weigh ratio of aluminum and clay material is from 1:99 to 55:45. The active metals comprise metals of VIII group and VIB group. The hydrogenation depickling catalyst preferably comprises magnesium oxide auxiliary agent or zinc oxide auxiliary agent. The invention has the advantages that: the cost is low, the usage performance is good, and the catalyst of the invention is useful in treatment of various heavy acid-containing hydrocarbon oil raw materials. The catalyst of the invention can be applied to the treating process of hydrogenation depickling of acid-containing crude oils, acid-containing heavy oils or acid-containing residual oils.
Description
Technical field
The present invention relates to a kind of acid-containing hydrocarbon oil hydrotreating catalyst and application thereof, more specifically about a kind of acid-containing hydrocarbon oil hydrogenation deacidification catalyst and application thereof.
Background technology
Acidic materials in oil comprise that aliphatic acid, aphthenic acids, aromatic acid and other material such as mercaptan, phenols, hydrogen sulfide, inorganic acid etc. are referred to as petroleum acids, account for the 1-2% of crude oil, and aphthenic acids account for 90% left and right of petroleum acids.Aphthenic acids normally is present in naphthene base crude with the complicated organic acid form of five yuan or hexa-atomic saturated cyclic structure, and content is less in intermediate base and paraffinic base crude oil.Concentration or the content of petroleum acids represent with total acid number.During total acid number (TAN) refers to and the milligram number of 1 gram crude oil or the needed potassium hydroxide of all acidic components of petroleum distillate (KOH), unit is mg KOH/g.
In petroleum refining process, the aphthenic acids in oil can be directly and iron react, cause the refining equipment corrosion such as furnace tubing; Also can with refining equipment on diaphragm FeS react, make hardware expose new surface, be subject to new corrosion.At present, common refining equipment only can be processed total acid number less than the hydrocarbon ils of 0.3mgKOH/g, will cause remarkable corrosion to refining equipment when total acid number reaches 0.5mgKOH/g, and when the total acid number in acid-containing hydrocarbon oil surpassed 1mgKOH/g, equipment corrosion can be very serious.
Along with the continually developing and exploiting of crude oil with high acid value in world wide, the output of world's Crude Oil Market crude oil with high acid value accounts for 5% left and right of total output, and annual also with 0.3% speed increase.Along with the continuous increase of the output of acid-containing raw oil, the equipment corrosion problem that is caused by acid-containing hydrocarbon oil also more and more receives people's concern.The method of acid-containing hydrocarbon oil depickling generally has physical absorption, solvent extraction, chemical conversion, and the most frequently used still chemical conversion process is as pyrolysis, hydrogenation deacidification etc.
Hydrotreating catalyst generally is comprised of metal, metal oxide and/or the metal sulfide that the alumina support load has a hydrogenating function.But conventional hydrotreating catalyst mainly designs in order to remove the impurity such as metal in raw material, sulphur, nitrogen, although can be used for hydrogenation deacidification, deacidification effect is undesirable.
USP5897769 has reported that use aperture hydrogenation catalyst (aperture 5-8.5nm) hydrogenation selectivity removes the method for oil low-molecular-weight aphthenic acids, and reaction temperature is 200-370 ℃.Crude oil and hydrogen and aperture Hydrobon catalyst haptoreaction, the molecular weight in crude oil generates CO, CO less than 450 naphthenic acid decomposition
2, H
2O and low-molecular-weight petroleum hydrocarbon.By the catalyzed conversion of petroleum acids, reduce the total acid number in oil.This technique can only the low-molecular-weight aphthenic acids of hydrotreatment (molecular weight is 250-400), and stays macromolecular aphthenic acids, is not suitable for containing the acid-containing hydrocarbon oil of higher resin and asphalt.
CN1590511A discloses a kind of distillate hydrogenation deacidifying catalyst.This catalyst contain aluminium oxide, magnesia and be selected from molybdenum and/or tungsten and nickel and/the hydrogenation active metals component of cobalt, wherein aluminium oxide by little porous aluminum oxide and macroporous aluminium oxide form composite alumina, make the aperture account for more than 75% of total pore volume at the pore volume of 4-10nm, guarantee with this pore-size distribution that catalyst is suitable.The raw material of this catalyst treatment is distillate, is not suitable for for macromolecular residual oil raw material.
Although the molecular weight less that contains acid constituents in some acid-containing hydrocarbon oil raw material, but owing to comprising heavy component, and these heavy components can stop up the aperture of aperture under reaction condition, are unfavorable for that the acid constituents that contains of molecular weight enters the catalyst duct and carries out the depickling reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of hydrocarbon oil hydrogenation depickling catalyst with higher depickling activity and its preparation method and application.
Hydrogenation deacidification catalyst of the present invention comprises carrier and active metal component, and carrier comprises aluminium oxide and clay material, and the weight ratio of aluminium oxide and clay material is 1: 99-55: 45.Clay material in the present invention can be selected one or more of kaolin, imvite, diatomite, attapulgite etc.Active metal component comprises VIII and vib metal, the VIII metal is Ni or Co, vib metal is W or Mo, active metal component is take the weight content of oxide in the hydrogenation deacidification catalyst as 1%～25%, be preferably 2%～10%, wherein VIII metal (take metal oxide) is 0wt%～9wt%, and vib metal (take metal oxide) is 0wt%～20wt%.The pore volume of hydrogenation deacidification catalyst is: 0.2～0.8ml/g, and preferred 0.2～0.5ml/g, specific area is 70～300m
2/ g, preferred 70～220m
2/ g.Main pore size distribution is as follows: the pore volume in bore dia＜6nm hole accounts for the ratio of total pore volume＜30%, and the pore volume in bore dia＞20nm hole accounts for the ratio of total pore volume＞10%.
Can comprise suitable auxiliary agent in hydrogenation deacidification catalyst of the present invention, as one or more in P, B, Ti, Zr etc.Auxiliary agent can add in the carrier preparation process, also can add when the dipping active metal component.Most preferably introduce auxiliary agent magnesia or zinc oxide in catalyst, the content in catalyst is 0.1wt%-5.0wt%.
Hydrogenation deacidification catalyst of the present invention adopts conventional infusion process preparation, as clay material, aluminium oxide or aluminium oxide precursor are mixed, adds suitable peptizing agent, additive, and then moulding, drying, roasting obtain the hydrogenation deacidification catalyst carrier.With this carrier impregnation reactive metal solution, then dry, roasting obtains the hydrogenation deacidification catalyst, and required auxiliary agent can be introduced in the carrier preparation process or introduce when the dipping reactive metal.Said catalyst carrier preparation process and condition can be undertaken by this area commonsense method.
Aluminium oxide precursor in hydrogenation deacidification catalyst of the present invention can be boehmite, and additive comprises expanding agent, extrusion aid, can use as required etc.The drying condition of carrier is under 80～200 ℃ dry 2～20 hours, and roasting condition is 450～900 ℃ of lower roastings 1～8 hour.Extrusion or make ball-type, dipping reactive metal solution after drying and roasting, then obtain catalyst through drying and roasting.The catalyst baking temperature is normal temperature～120 ℃, drying time 0.5～24h, 400～550 ℃ of sintering temperatures, roasting time 1～6h.Described expanding agent is one or more of carbon black, ammonium phosphate, ammonium carbonate, polyethylene glycol, polyvinyl alcohol, methylcellulose, polyacrylamide etc.
The application of hydrocarbon oil hydrogenation depickling catalyst of the present invention in the acid-containing hydrocarbon oil hydrogenation deacidification, concrete application conditions can for: reaction temperature is 200～390 ℃, reaction pressure is 1～15MPa, hydrogen to oil volume ratio 100～1000, and liquid volume air speed (LHSV) is 0.5～5h
-1The concrete technology condition can be determined according to the character such as the content acid of acid-containing hydrocarbon oil and depickling index request.Can be applied to the hydrogenation deacidification of various acid-containing hydrocarbon oils, the depickling that is particularly suitable for acid-containing raw oil, contains sour mink cell focus or contains acid residual oil is processed.Catalyst vulcanized before for the hydrogenation deacidification reaction, made reactive metal and metal promoter change sulphided state into, and sulfuration can be adopted vulcanization process known by the technical staff.
Catalyst provided by the invention adopts suitable carrier material, coordinates reactive metal and the auxiliary agent of suitable composition and content, has obtained the deacidification effect of the feedstock oils such as good mink cell focus or residual oil.Simultaneously, clay material mixes with aluminium oxide, has reduced the cost of catalyst, has satisfied simultaneously the requirement of hydrocarbon oil hydrogenation deacidifying process.
The specific embodiment
Further explain technical characterictic of the present invention below by embodiment, but be not limited to embodiment, percentage composition wherein by weight percentage.
Embodiment 1-6 illustrates hydrogenation deacidification Catalysts and its preparation method of the present invention.
Embodiment 1
Take respectively the 70 dried glue of gram boehmite (salic 73wt%) and 50 gram kaolin, add 1.41 gram carbon blacks, 1.41 gram sesbania powder, mix, then add ammoniacal liquor 9.78 grams, add distilled water 70 grams, the kneading extruded moulding, then at 120 ℃ of dry 2h, 800 ℃ of roasting 3h obtain carrier A.
Take ammonium heptamolybdate 82.11 grams, adding 900ml concentration is 12% ammoniacal liquor, then adds basic nickel carbonate 27.94 grams to be stirred to dissolving fully, with ammoniacal liquor, liquor capacity is adjusted to 1000ml, gets solution L-1.With the carrier A saturated dipping of solution L-1 solution, at 110 ℃ of dry 2h, 500 ℃ of roasting 5h obtain catalyst T-A.
Embodiment 2
Method is with embodiment 1, and the amount of just adding into basic magnesium carbonate is 1.94 grams, and at 120 ℃ of dry 2h, 600 ℃ of roasting 2h obtain carrier B.With the carrier B saturated dipping of solution L-1 solution, at 120 ℃ of dry 2h, 480 ℃ of roasting 3h obtain catalyst T-B.
Embodiment 3
Take respectively the 40 dried glue of gram boehmite (salic 73wt%) and 70 gram imvites, add 2.52 gram carbon blacks, 2.52 gram sesbania powder and 3.52 gram ammonium carbonates, mix, then add 65 gram distilled water, the kneading extruded moulding, then at 100 ℃ of dry 3h, 600 ℃ of roasting 1h obtain support C.
Take ammonium heptamolybdate 53.30 grams, adding 900ml concentration is 12% ammoniacal liquor, then adds basic nickel carbonate 18.14 grams to be stirred to dissolving fully, with ammoniacal liquor, liquor capacity is adjusted to 1000ml, gets solution L-2.With the saturated dipping of support C L-2 solution, at 100 ℃ of dry 6h, 520 ℃ of roasting 3h obtain catalyst T-C.
Embodiment 4
Take respectively the 15 dried glue of gram boehmite (salic 73wt%) and 45 gram kaolin and 45 gram diatomite, add 5.03 gram carbon blacks, 2.01 gram sesbania powder, mix, then take 5.64 gram polyethylene glycol, with joining in raw material after 41 gram distilled water dissolvings, the kneading extruded moulding, then at 110 ℃ of dry 3h, 850 ℃ of roasting 1h obtain carrier D.
Take ammonium heptamolybdate 53.30 grams, adding 900ml concentration is 12% ammoniacal liquor, then adds basic cobaltous carbonate 16.80 grams to be stirred to dissolving fully, with ammoniacal liquor, liquor capacity is adjusted to 1000ml, gets solution L-3.With the saturated dipping of carrier D L-3 solution, at 120 ℃ of dry 5h, 420 ℃ of roasting 4h obtain catalyst T-D.
Embodiment 5
Take respectively the 35 dried glue of gram boehmite (salic 73wt%) and 55 gram imvites and 20 gram diatomite, add 2.01 gram carbon blacks, 2.01 gram sesbania powder, mix, then take 5.04 gram carbonic hydroammonium, with joining in raw material after 40 gram distilled water dissolvings, the kneading extruded moulding, then at 100 ℃ of dry 3h, 750 ℃ of roasting 3h obtain carrier E.
Take ammonium heptamolybdate 12.82 grams, adding 900ml concentration is 12% ammoniacal liquor, then adds basic nickel carbonate 4.36 grams to be stirred to dissolving fully, with ammoniacal liquor, liquor capacity is adjusted to 1000ml, gets solution L-4.With the saturated dipping of carrier E L-4 solution, at 120 ℃ of dry 2h, 480 ℃ of roasting 3h obtain catalyst T-E.
Embodiment 6
Method is with embodiment 5, and just adding into its amount of zinc nitrate is 4.03 grams, and at 120 ℃ of dry 2h, 700 ℃ of roasting 2h obtain carrier F.With the carrier F saturated dipping of solution L-4 solution, at 110 ℃ of dry 2h, 450 ℃ of roasting 4h obtain catalyst T-F.
Comparative Examples 1
Require Kaolinite Preparation of Catalyst according to USP5897769.Take the 100 dried glue of gram boehmite (salic 73wt%), add 3.65 gram carbon blacks, 1.46 gram sesbania powder, mix, then add ammoniacal liquor 1.43 grams, add distilled water 100 grams, the kneading extruded moulding, then at 120 ℃ of dry 2h, 600 ℃ of roasting 3h obtain carrier G.With the carrier G saturated dipping of solution L-1 solution, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst T-G.
Comparative Examples 2
Require Kaolinite Preparation of Catalyst according to CN1590511A.Take respectively the 50 dried glue of gram macropore boehmite (salic 73wt%) and the 50 dried glue of gram aperture boehmite (salic 81wt%), after mixing, add 3.65 gram carbon blacks, 1.46 gram sesbania powder, then add ammoniacal liquor 1.43 grams, add distilled water 105 grams, the kneading extruded moulding, then at 120 ℃ of dry 2h, 600 ℃ of roasting 3h obtain carrier H.With the carrier H saturated dipping of solution L-1 solution, at 110 ℃ of dry 2h, 500 ℃ of roasting 3h obtain catalyst T-H.
The physicochemical property of catalyst is as shown in table 1.
The physicochemical property of table 1 catalyst
Embodiment 7-12 explanation the invention provides the hydrogenation deacidification performance of catalyst, and the character that contains acid starting material is as shown in table 2.
Table 2 contains the character of acid starting material
Contain acid starting material and hydrogen enters fixed bed hydrogenation reactor, contact with contrast medium T-G, T-H with 100ml hydrogenation deacidification catalyst T-A, T-B, T-C, T-D, T-E, T-F respectively and carry out hydrogenation reaction.Carrying out before the hydrogenation deacidification reaction, catalyst being carried out vulcanizing treatment, conditions of vulcanization is for to use the kerosene that contains carbon disulfide 2.5wt% to be sulfurized oil, and during sulfuration, pressure is 4.5MPa, and during sulfuration fluid, volume space velocity is 1.5h
-1, hydrogen to oil volume ratio is 500, and sulfuration is 12 hours under 280 ℃ of conditions, and sulfuration is 24 hours under 320 ℃ of conditions, so advances swap-in sulfur acid hydrocarbon ils and carries out the hydrogenation deacidification reaction.The hydrogenation deacidification reaction temperature is respectively 320 ℃, reaction pressure 4.5MPa, and hydrogen to oil volume ratio 500, liquid volume air speed (LHSV) is 2.0h
-1, after reaction, the acid removal rate of oil product sees Table 3.
Total acid number in product after table 3 hydrogenation deacidification
As can be seen from Table 3: adopt aluminium oxide and clay to be mixed with the catalyst deacidification effect that obtains better, the catalyst cost is lower, is applicable to the deacidifying process of acid-containing raw oil.
Claims (5)
1. hydrocarbon oil hydrogenation depickling catalyst, the hydrogenation deacidification catalyst comprises carrier and active metal component, it is characterized in that: carrier comprises aluminium oxide and clay material, the weight ratio of aluminium oxide and clay material is 1: 99-55: 45, active metal component comprises VIII and vib metal, the VIII metal is Ni or Co, vib metal is W or Mo, active metal component is take the weight content of oxide in the hydrogenation deacidification catalyst as 1%～25%, the pore volume of hydrogenation deacidification catalyst is: 0.2～0.8ml/g, specific area is 70～300m
2/ g; Described clay material is selected one or more in kaolin, imvite, diatomite and attapulgite; Contain auxiliary agent zinc oxide in the hydrogenation deacidification catalyst, the content in the hydrogenation deacidification catalyst is 0.1wt%-5.0wt%.
2. according to catalyst claimed in claim 1, it is characterized in that: the weight content in catalyst is 2%～10% to active metal component take oxide.
3. the application of the described arbitrary hydrocarbon oil hydrogenation depickling catalyst of claim 1 to 2 in the acid-containing hydrocarbon oil hydrogenation deacidification.
4. according to application claimed in claim 3, it is characterized in that: acid-containing hydrocarbon oil hydrogenation deacidification application conditions is: reaction temperature is 200～390 ℃, and reaction pressure is 1～15MPa, hydrogen to oil volume ratio 100～1000, and the liquid volume air speed is 0.5～5h
-1
5. according to the described application of claim 3 or 4, it is characterized in that: acid-containing hydrocarbon oil is acid-containing raw oil, contains sour mink cell focus or contain acid residual oil.
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| CN102380391A (en) * | 2010-08-26 | 2012-03-21 | 中科合成油技术有限公司 | Selective deacidification catalyst, preparation method thereof and application thereof to selective hydrogenation deacidification treatment of Fisher-Tropsch synthetic oil |
| CN105944750B (en) * | 2016-05-06 | 2019-05-17 | 中石化炼化工程（集团）股份有限公司 | A kind of highly selective oil hydrogenation decarboxylation catalyst and preparation method thereof |
| CN106582731A (en) * | 2016-12-14 | 2017-04-26 | 钦州学院 | Deacidification catalyst and preparation method thereof |
| CN109759060B (en) * | 2019-02-25 | 2021-11-26 | 华谊高新纯化技术(大连)有限公司 | Mixed carbon four-component selective hydrogenation catalyst and preparation method thereof |
| CN111822057B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of spherical alumina carrier |
| CN111821986B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation carbon residue removal catalyst |
| CN114917918A (en) * | 2022-06-21 | 2022-08-19 | 临沭县华盛化工有限公司 | Special iron-molybdenum catalyst in hydrocyanic acid production process and preparation method |
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|---|---|---|---|---|
| US4203829A (en) * | 1978-09-28 | 1980-05-20 | Standard Oil Company (Indiana) | Catalyst, method of preparation and use thereof in hydrodesulfurizing cracked naphtha |
| CN1590511A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Fraction oil hydrogenation and acid removing eatalyst |
| CN101491764A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and preparation method and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203829A (en) * | 1978-09-28 | 1980-05-20 | Standard Oil Company (Indiana) | Catalyst, method of preparation and use thereof in hydrodesulfurizing cracked naphtha |
| CN1590511A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Fraction oil hydrogenation and acid removing eatalyst |
| CN101491764A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and preparation method and use thereof |
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