EP2001976A1 - A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstock - Google Patents
A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstockInfo
- Publication number
- EP2001976A1 EP2001976A1 EP06725538A EP06725538A EP2001976A1 EP 2001976 A1 EP2001976 A1 EP 2001976A1 EP 06725538 A EP06725538 A EP 06725538A EP 06725538 A EP06725538 A EP 06725538A EP 2001976 A1 EP2001976 A1 EP 2001976A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- feedstock
- tan
- catalyst
- acid number
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 9
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010779 crude oil Substances 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004438 BET method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
- C10G2300/203—Naphthenic acids, TAN
Definitions
- the present invention provides a process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, in particular crude oil.
- TAN total acid number
- TAN total acid number
- catalysts that are essentially free of the hydrogenating components that are typically used for hydroconversion reactions such as hydrodesulphurisation, hydrodenitrogenation, and hydrocracking, i.e. compounds of metals of any one of Columns 5 to 10 of the Periodic Table of Elements, can be used for the selective hydrogenation of acids in liquid hydrocarbonaceous streams, in particular crude oil.
- the present invention provides a process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, wherein the feedstock is contacted, in the presence of a hydrogen-containing gas and at a temperature in the range of from 200 to 400 0 C and at elevated pressure, with a catalyst comprising an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof, to obtain a liquid hydrocarbonaceous product with a reduced total acid number.
- TAN total acid number
- An advantage of the process according to the invention is that the total acid number of the feedstock is reduced by hydrogenation whilst other hydrogenation reactions such as hydrodesulphurisation, hydrodenitrogenation and saturation of unsaturated hydrocarbons are minimised.
- a liquid hydrocarbonaceous feedstock is contacted, in the presence of a hydrogen-containing gas at a temperature in the range of from 200 to 400 0 C and at elevated pressure, with a catalyst comprising an oxide of a Column 3 or 4 metal or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof.
- the feedstock may be any liquid hydrocarbonaceous stream comprising carboxylic, i.e. organic, acids.
- the process is particularly suitable for feedstocks comprising naphthenic acids.
- the feedstock is a crude oil, a distillate stream such as naphtha or gasoil, a residue fraction of an atmospheric crude oil distillation or a hydrocarbonaceous distillate product not meeting TAN product specifications, such as for example heating oil.
- the process according to the invention is particularly suitable for the reduction of the total acid number of crude oil.
- the hydrogen-containing gas is preferably hydrogen or synthesis gas.
- the use of synthesis gas as hydrogen- containing gas is particularly advantageous in a situation wherein no hydrogen gas is available, for example at remote places such as off-shore oil platforms.
- the temperature and pressure at which the feedstock is contacted with the catalyst is such that hydrogenation of carboxylic acids takes place, i.e. at least 200 0 C.
- the temperature is below the temperature at which thermal decomposition of carboxylic acids occurs, i.e. below 400 0 C.
- the temperature is in the range of from 250 to 390 0 C, more preferably of from 300 to 380 °C. - A -
- the process is performed at elevated pressure, i.e. above atmospheric pressure.
- the pressure is in the range of from 2 to 200 bar g, more preferably of from 10 to 150 bar g, even more preferably of from 25 to 120 bar g.
- the catalyst comprises an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements (latest IUPAC notation) or of a lanthanide.
- the oxide may also be a mixed oxide of two or more of such metals.
- the catalyst may also comprise a mixture of two or more of such oxides.
- the catalyst is essentially free of metals of Columns 5 to 10 of the Periodic Table of Elements (latest IUPAC notation) or of compounds thereof.
- Reference herein to a catalyst essentially free of certain compounds is to a catalyst that is free of such compounds except for minimal amounts, typically in the ppm range or lower, that may be present as unintentional contaminants or as left-overs from a mineral ore refining process for obtaining the oxide of the Column 3 or 4 metal or lanthanide.
- the catalyst comprises an oxide of a Column 4 metal or of a lanthanide.
- Preferred Group 4 metal oxides are titanium oxide and zirconium oxide, a preferred oxide of a lanthanide is ceria. More preferably, the catalyst consists of titanium oxide and/or zirconium oxide, even more preferably of zirconium oxide .
- the catalyst may be prepared by any preparation method known in the art.
- the catalyst is prepared such that its specific surface area is at least
- the feedstock for the process according to the invention preferably has a total acid number of at least 0.2 mg KOH/g feedstock, preferably at least 0.5 mg KOH/ g feedstock, more preferably at least 1.0 mg KOH/ g feedstock.
- Reference herein to the total acid number is to the amount of KOH (in mg) per gram feedstock as determined by ASTM D664.
- the liquid hydrocarbonaceous product has preferably a TAN of at most 0.2 mg KOH/g feedstock, more preferably at most 0.1 mg KOH/g feedstock, even more preferably at most 0.05 mg KOH/g feedstock.
- the TAN is preferably reduced to such extent that the liquid hydrocarbonaceous product with a reduced total acid number has at most 50% of the TAN of the feedstock, more preferably at most 30%.
- crude oil was contacted with a solid inert material (0.1 mm silicon carbide particles) or with one of the catalysts described below (catalyst particles diluted with silicon carbide particles: 1/1 v/v) in the presence of a hydrogen-containing gas or nitrogen for at least 100 hours.
- a solid inert material 0.1 mm silicon carbide particles
- catalysts described below catalyst particles diluted with silicon carbide particles: 1/1 v/v
- TAN total acid number
- Experiments 3, 4, 6, 7, 9, 10, 12 and 14 to 16 are experiments according to the invention.
- Experiments 1, 2, 5, 8, 11, and 13 are comparison experiments.
- Titania catalyst 1 Titania catalyst 1
- a titania catalyst further referred to as titania 1 was prepared as follows. An amount of 3192 grams of titania powder (P25, ex. Degussa; loss on ignition: 4.4 wt% at 540 0 C) was mixed with 100 grams oxalic acid dihydrate in a mix-muller kneader (Simpson) . After 4 minutes of mix-mulling, 981 grams of de-ionised water and 100 grams of polyethylene glycol were added and mix- mulling was continued for another 12 minutes. Then, 100 grams of methyl cellulose were added and mix-mulling was continued for another 20 minutes. The thus-formed mixture was shaped by extrusion through a 1.7 mm diameter trilobe-shaped die-plate. The trilobes were dried for 2 hours at 120 0 C and calcined for 2 hours at 500 0 C.
- the resulting titania trilobes have a surface area of 52 m2/g as measured by nitrogen adsorption
- Titania catalyst 2 (BET method) and a pore volume of 0.31 ml/g as measured by mercury intrusion. Titania catalyst 2
- Titania particles commercially available as X096 (ex. CRI Catalyst Company) were used as titania catalyst (further referred to as titania 2) . These titania particles have a surface area of 120 m ⁇ /g as measured by nitrogen adsorption (BET method) and a pore volume of 0.32 ml/g as measured by mercury intrusion.
- Zirconia catalyst commercially available as X096 (ex. CRI Catalyst Company) were used as titania catalyst (further referred to as titania 2) . These titania particles have a surface area of 120 m ⁇ /g as measured by nitrogen adsorption (BET method) and a pore volume of 0.32 ml/g as measured by mercury intrusion.
- BET method nitrogen adsorption
- a zirconia catalyst was prepared as follows. An amount of 264 grams of zirconia powder (RClOO, ex. Daiichi; loss on ignition: 5.3 wt% at 540 0 C) was mixed with 90 grams of a solution of 5 wt% polyvinyl alcohol in de-ionised water in a kneader (Werner&Pfeider Sigma kneader type LUK 0.75) . After 7 minutes of kneading, 2.5 grams of a cationic poly acryl amide (Superfloc, ex. Cytec) were added and after 20 minutes of kneading 8 grams of de-ionised water were added. The mixture was kneaded for another 22 minutes. The thus-formed mixture was shaped by extrusion into 1.7 mm diameter trilobes. The extrudates were dried for 2 hours at 120 0 C and calcined for 2 hours at 550 0 C.
- the resulting zirconia trilobes have a surface area of 54 m ⁇ /g as measured by nitrogen adsorption
- a conventional hydrodesulphurisation catalyst comprising Ni and Mo on alumina which is commercially available as CRITERION RM-5030 (ex. Criterion Catalyst Company) , was used.
- a WHV weight hourly velocity, i.e. kg oil/kg catalyst/hour.
- the weight hourly velocity of the oil was 1.1 kg/kg SiC/h in experiments 1 and 2) .
- b gas rate in normal litres gas per kg oil.
- c TAN in mg KOH/g oil. d not determined; liquid effluent did not have a smell of hydrogen sulphide. e not determined; liquid effluent had a smell of hydrogen sulphide.
- f syngas composition 33.2 vol% hydrogen; 20.7 vol% CO; balance nitrogen.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, wherein the feedstock is contacted, in the presence of a hydrogen-containing gas and at a temperature in the range of from 200 to 400 °C and at elevated pressure, with a catalyst comprising an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof, to obtain a liquid hydrocarbonaceous product with a reduced total acid number.
Description
A PROCESS FOR REDUCING THE TOTAL ACID NUMBER (TAN) OF A LIQUID HYDROCARBONACEOUS FEEDSTOCK
Field of the invention
The present invention provides a process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, in particular crude oil. Background of the invention
Crude oil and other liquid hydrocarbonaceous streams with a high amount of acids are difficult to refine. Especially in the distillation unit of a crude oil refinery, a high amount of acids leads to corrosion problems. It is known that acids are removed by hydrotreating, i.e. the same process wherein other heteroatoms like sulphur and nitrogen are removed from liquid hydrocarbonaceous feedstocks. Hydrotreating, however, is a process that is carried out downstream of the distillation unit in a refinery.
In order to avoid corrosion problems resulting from the acid content of the crude oil, different crude oil streams are typically blended to obtain a crude oil feedstock with an acceptable amount of acids. The acid content of a crude oil or of other hydrocarbonaceous liquids is generally expressed as the total acid number (TAN) of such liquid. The TAN represents milligrams KOH per gram liquid needed to neutralise the acid according to a procedure described in ASTM D664.
There is a need in the art for a process that is able to reduce the TAN of liquid hydrocarbonaceous streams such as crude oil that are used as feedstock in
refineries, with minimum conversion of sulphur- and nitrogen-containing compounds and unsaturated hydrocarbons. By such process, an acceptable refinery feedstock would be obtained with minimal hydrogen consumption.
Summary of the invention
It has been found that catalysts that are essentially free of the hydrogenating components that are typically used for hydroconversion reactions such as hydrodesulphurisation, hydrodenitrogenation, and hydrocracking, i.e. compounds of metals of any one of Columns 5 to 10 of the Periodic Table of Elements, can be used for the selective hydrogenation of acids in liquid hydrocarbonaceous streams, in particular crude oil. Accordingly, the present invention provides a process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, wherein the feedstock is contacted, in the presence of a hydrogen-containing gas and at a temperature in the range of from 200 to 400 0C and at elevated pressure, with a catalyst comprising an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof, to obtain a liquid hydrocarbonaceous product with a reduced total acid number.
An advantage of the process according to the invention is that the total acid number of the feedstock is reduced by hydrogenation whilst other hydrogenation reactions such as hydrodesulphurisation, hydrodenitrogenation and saturation of unsaturated hydrocarbons are minimised.
Detailed description of the invention
In the process according to the invention, a liquid hydrocarbonaceous feedstock is contacted, in the presence of a hydrogen-containing gas at a temperature in the range of from 200 to 400 0C and at elevated pressure, with a catalyst comprising an oxide of a Column 3 or 4 metal or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof.
The feedstock may be any liquid hydrocarbonaceous stream comprising carboxylic, i.e. organic, acids. The process is particularly suitable for feedstocks comprising naphthenic acids. Preferably, the feedstock is a crude oil, a distillate stream such as naphtha or gasoil, a residue fraction of an atmospheric crude oil distillation or a hydrocarbonaceous distillate product not meeting TAN product specifications, such as for example heating oil. The process according to the invention is particularly suitable for the reduction of the total acid number of crude oil. The hydrogen-containing gas is preferably hydrogen or synthesis gas. The use of synthesis gas as hydrogen- containing gas is particularly advantageous in a situation wherein no hydrogen gas is available, for example at remote places such as off-shore oil platforms. The temperature and pressure at which the feedstock is contacted with the catalyst is such that hydrogenation of carboxylic acids takes place, i.e. at least 200 0C. The temperature is below the temperature at which thermal decomposition of carboxylic acids occurs, i.e. below 400 0C. Preferably, the temperature is in the range of from 250 to 390 0C, more preferably of from 300 to 380 °C.
- A -
The process is performed at elevated pressure, i.e. above atmospheric pressure. Preferably, the pressure is in the range of from 2 to 200 bar g, more preferably of from 10 to 150 bar g, even more preferably of from 25 to 120 bar g.
The catalyst comprises an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements (latest IUPAC notation) or of a lanthanide. The oxide may also be a mixed oxide of two or more of such metals. The catalyst may also comprise a mixture of two or more of such oxides. The catalyst is essentially free of metals of Columns 5 to 10 of the Periodic Table of Elements (latest IUPAC notation) or of compounds thereof. Reference herein to a catalyst essentially free of certain compounds is to a catalyst that is free of such compounds except for minimal amounts, typically in the ppm range or lower, that may be present as unintentional contaminants or as left-overs from a mineral ore refining process for obtaining the oxide of the Column 3 or 4 metal or lanthanide.
Preferably, the catalyst comprises an oxide of a Column 4 metal or of a lanthanide. Preferred Group 4 metal oxides are titanium oxide and zirconium oxide, a preferred oxide of a lanthanide is ceria. More preferably, the catalyst consists of titanium oxide and/or zirconium oxide, even more preferably of zirconium oxide .
The catalyst may be prepared by any preparation method known in the art. Preferably, the catalyst is prepared such that its specific surface area is at least
10 m2/g, more preferably at least 30 m^/g.
The feedstock for the process according to the invention preferably has a total acid number of at least
0.2 mg KOH/g feedstock, preferably at least 0.5 mg KOH/ g feedstock, more preferably at least 1.0 mg KOH/ g feedstock. Reference herein to the total acid number is to the amount of KOH (in mg) per gram feedstock as determined by ASTM D664.
The liquid hydrocarbonaceous product has preferably a TAN of at most 0.2 mg KOH/g feedstock, more preferably at most 0.1 mg KOH/g feedstock, even more preferably at most 0.05 mg KOH/g feedstock. The TAN is preferably reduced to such extent that the liquid hydrocarbonaceous product with a reduced total acid number has at most 50% of the TAN of the feedstock, more preferably at most 30%. Example Hydrogenation process
In a microflow reactor, crude oil was contacted with a solid inert material (0.1 mm silicon carbide particles) or with one of the catalysts described below (catalyst particles diluted with silicon carbide particles: 1/1 v/v) in the presence of a hydrogen-containing gas or nitrogen for at least 100 hours. Two different crude oils were used. For experiments 1 to 8 and 13 to 16, a West- African crude oil was used (crude 1); for experiments 9 to 12, a crude oil from the Middle-East was used (crude 2) . The specifications of both crude oils are shown in table 1. The exact conditions for each experiment are given in table 2.
The total acid number (TAN) of the liquid effluent of each of the experiments was determined according to ASTM D664. The hydrogen sulphide concentration in the vapour phase effluent was determined by gas chromatography. TAN of the liquid effluent and the
hydrogen sulphide concentration in the vapour phase effluent are also shown in table 2.
Experiments 3, 4, 6, 7, 9, 10, 12 and 14 to 16 are experiments according to the invention. Experiments 1, 2, 5, 8, 11, and 13 are comparison experiments.
Table 1 Crude oil specification
Catalysts
The following catalysts were used in the hydrogenation experiments. Titania catalyst 1
A titania catalyst further referred to as titania 1 was prepared as follows. An amount of 3192 grams of titania powder (P25, ex. Degussa; loss on ignition: 4.4 wt% at 540 0C) was mixed with 100 grams oxalic acid dihydrate in a mix-muller kneader (Simpson) . After 4 minutes of mix-mulling, 981 grams of de-ionised water and 100 grams of polyethylene glycol were added and mix- mulling was continued for another 12 minutes. Then, 100 grams of methyl cellulose were added and mix-mulling was continued for another 20 minutes. The thus-formed
mixture was shaped by extrusion through a 1.7 mm diameter trilobe-shaped die-plate. The trilobes were dried for 2 hours at 120 0C and calcined for 2 hours at 500 0C.
The resulting titania trilobes have a surface area of 52 m2/g as measured by nitrogen adsorption
(BET method) and a pore volume of 0.31 ml/g as measured by mercury intrusion. Titania catalyst 2
Titania particles commercially available as X096 (ex. CRI Catalyst Company) were used as titania catalyst (further referred to as titania 2) . These titania particles have a surface area of 120 m^/g as measured by nitrogen adsorption (BET method) and a pore volume of 0.32 ml/g as measured by mercury intrusion. Zirconia catalyst
A zirconia catalyst was prepared as follows. An amount of 264 grams of zirconia powder (RClOO, ex. Daiichi; loss on ignition: 5.3 wt% at 540 0C) was mixed with 90 grams of a solution of 5 wt% polyvinyl alcohol in de-ionised water in a kneader (Werner&Pfeider Sigma kneader type LUK 0.75) . After 7 minutes of kneading, 2.5 grams of a cationic poly acryl amide (Superfloc, ex. Cytec) were added and after 20 minutes of kneading 8 grams of de-ionised water were added. The mixture was kneaded for another 22 minutes. The thus-formed mixture was shaped by extrusion into 1.7 mm diameter trilobes. The extrudates were dried for 2 hours at 120 0C and calcined for 2 hours at 550 0C.
The resulting zirconia trilobes have a surface area of 54 m^/g as measured by nitrogen adsorption
(BET method) and a pore volume of 0.35 ml/g as measured by mercury intrusion.
NiMo on alumina
A conventional hydrodesulphurisation catalyst comprising Ni and Mo on alumina, which is commercially available as CRITERION RM-5030 (ex. Criterion Catalyst Company) , was used.
Table 2 Process conditions; TAN in liquid effluent and H2S in vapour effluent.
Table 2 (cont'd) Process conditions; TAN in liquid effluent and H2S in vapour effluent.
a WHV : weight hourly velocity, i.e. kg oil/kg catalyst/hour. In experiments 1 and 2, no catalyst was present and no comparable WHV could be defined (the weight hourly velocity of the oil was 1.1 kg/kg SiC/h in experiments 1 and 2) . b gas rate in normal litres gas per kg oil. c TAN in mg KOH/g oil. d not determined; liquid effluent did not have a smell of hydrogen sulphide. e not determined; liquid effluent had a smell of hydrogen sulphide. f syngas composition: 33.2 vol% hydrogen; 20.7 vol% CO; balance nitrogen.
Claims
1. A process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock, wherein the feedstock is contacted, in the presence of a hydrogen- containing gas and at a temperature in the range of from 200 to 400 0C and at elevated pressure, with a catalyst comprising an oxide of a metal of Column 3 or 4 of the Periodic Table of Elements or of a lanthanide, which catalyst is essentially free of Column 5 to 10 metals or compounds thereof, to obtain a liquid hydrocarbonaceous product with a reduced total acid number.
2. A process according to claim 1, wherein the oxide is an oxide of a Column 4 metal or of a lanthanide, preferably is titanium oxide or zirconium oxide, more preferably zirconium oxide.
3. A process according to claim 2, wherein the catalyst essentially consists of titanium oxide and/or zirconium oxide .
4. A process according to any one of the preceding claims, wherein the pressure is in the range of from 2 to 200 bar g, preferably of from 10 to 150 bar g, more preferably 25 to 120 bar g.
5. A process according to any one of the preceding claims, wherein the temperature is in the range of from 250 to 390 0C, preferably of from 300 to 380 0C.
6. A process according to any one of the preceding claims, wherein the hydrogen-containing gas is synthesis gas or hydrogen.
7. A process according to any one of the preceding claims, wherein the feedstock has a TAN of at least
0.2 mg KOH/g feedstock, preferably at least 0.5 rag KOH/ g feedstock, preferably at least 1.0 mg KOH/g feedstock.
8. A process according to any one of the preceding claims, wherein the liquid hydrocarbonaceous product has a TAN of at most 0.2 mg KOH/g feedstock, preferably at most 0.1 mg KOH/g feedstock, more preferably at most 0.05 mg KOH/g feedstock.
9. A process according to any one of the preceding claims, wherein the liquid hydrocarbonaceous product with a reduced total acid number has a TAN of at most 50% of the TAN of the crude oil product, preferably at most 30%.
10. A process according to any one of the preceding claims, wherein the liquid hydrocarbonaceous feedstock is crude oil.
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PCT/EP2006/061302 WO2007112782A1 (en) | 2006-04-04 | 2006-04-04 | A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstock |
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EP (1) | EP2001976A1 (en) |
JP (1) | JP5399234B2 (en) |
CN (1) | CN101405371B (en) |
AU (1) | AU2006341463A1 (en) |
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GB496779A (en) * | 1937-01-04 | 1938-12-06 | Bataafsche Petroleum | A process for removing naphthenic acids from mineral lubricating oils or lubricating oil fractions |
US3846288A (en) * | 1973-07-05 | 1974-11-05 | Gulf Research Development Co | Acid number reduction of hydrocarbon fractions using a solid catalyst and methanol |
US6547957B1 (en) * | 2000-10-17 | 2003-04-15 | Texaco, Inc. | Process for upgrading a hydrocarbon oil |
US20020148754A1 (en) * | 2001-02-08 | 2002-10-17 | Gong William H. | Integrated preparation of blending components for refinery transportation fuels |
NL1027769C2 (en) * | 2003-12-19 | 2006-07-13 | Shell Int Research | Systems, methods and catalysts for producing a crude product. |
JP2008504409A (en) * | 2004-07-07 | 2008-02-14 | カリフォルニア インスティテュート オブ テクノロジー | Process to improve oil using metal oxides |
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2006
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AU2006341463A1 (en) | 2007-10-11 |
CA2647760C (en) | 2013-12-10 |
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CN101405371A (en) | 2009-04-08 |
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