CN1071136C - A method for the demercaptanization of petroleum distillates - Google Patents
A method for the demercaptanization of petroleum distillates Download PDFInfo
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- CN1071136C CN1071136C CN95194720A CN95194720A CN1071136C CN 1071136 C CN1071136 C CN 1071136C CN 95194720 A CN95194720 A CN 95194720A CN 95194720 A CN95194720 A CN 95194720A CN 1071136 C CN1071136 C CN 1071136C
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- quality
- copper
- catalyst
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- mercaptan
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003209 petroleum derivative Substances 0.000 title abstract 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims description 30
- 150000004706 metal oxides Chemical class 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000004744 fabric Substances 0.000 claims description 23
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000003208 petroleum Substances 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- -1 phenylene ether ketone Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000002759 woven fabric Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
- 238000007670 refining Methods 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229930013930 alkaloid Natural products 0.000 description 3
- 150000003797 alkaloid derivatives Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- 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
- B01J21/18—Carbon
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Working-Up Tar And Pitch (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The demercaptanization of petroleum distillates may be carried out by means of the oxidation of the mercaptans contained therein using the oxygen in the air, at a temperature of about 80 to about 220 DEG C, in the presence of about 0.01 to about 10.0 mass % of a water-soluble salt of copper, iron, nickel, or cobalt, on a fibrous carbonaceous material in the form of a woven fabric, felt, rope, or twisted strand, used as a heterogeneous catalyst. The fibrous carbonaceous material used in the process contains oxides of calcium, magnesium, copper, manganese, iron, zinc, and aluminum in an amount of up to about 0.03 mass %.
Description
Background of invention
The present invention relates to remove from fraction oil of petroleum with oxidizing process the field of mercaptan sulfur, the present invention can be used for petroleum refining industry gasoline, kerosene and diesel oil distillate removal of mercaptans.
The method of fraction oil of petroleum removal of mercaptans is known, they relate in the presence of alkali and heterogeneous catalyst, make mercaptan oxidation with airborne oxygen, heterogeneous catalyst contains the phthalocyanine cobalt that is deposited on hard matrix such as active carbon, graphite, aluminium oxide, modenite, silica gel etc. or phthalocyanine vanadium (referring to Russian Patent 355805 and 654180; US4033860 and 4481106).
The major defect of described method is that in fraction oil of petroleum not high enough and this method of the degree of oxidation of mercaptan need consume a large amount of alkali.
From the viewpoint of technical spirit with the result who obtains, with the very similar method of method described herein be in the presence of 5～20% aqueous slkalis and heterogeneous phthalocyanine catalyst, make the method for high point petroleum fractional oil desulfurizing alcohol with airborne oxygen oxidation mercaptan, heterogeneous catalyst contains 0.005～0.9% (quality) phthalocyanine cobalt, and it is deposited on the carbon fibre shape material of carbon fibre or graphite fibre form.
The major defect of this method is the low and a large amount of alkaloid substances of needs consumption of mercaptan oxidation degree stability of catalytic activity not high enough, catalyst in fraction oil of petroleum.
Brief summary of the invention
The objective of the invention is to improve fraction oil of petroleum the removal of mercaptans degree, improve the stability of catalytic activity of catalyst and needn't use a large amount of alkali.
Therefore, according to the present invention, provide a kind of in the presence of heterogeneous catalyst by make the method for the fraction oil of petroleum removal of mercaptans that contains mercaptan with the described mercaptan of airborne oxygen oxidation, described method is included in the catalyst that contains water-soluble mantoquita, molysite, nickel salt or cobalt salt and exists down, described mercaptan is contacted with oxygen, the quantity of water soluble salt is about 0.01 to about 10% (quality), and it is deposited on the fibrous carbon material, and described material contains the oxide of different price metal; Described method is carried out to about 200 ℃ of scopes about 80.
According to the present invention, a kind of catalyst of fibrousness carbonaceous material also is provided, the oxide and about 0.01 that described material contains the different price metal is deposited on the described material to the water-soluble mantoquita of about 10.0% (quality), molysite, nickel salt or cobalt salt.
Detailed description of preferred embodiments
The method according to this invention by providing a kind of in the presence of heterogeneous catalyst, makes the method for fraction oil of petroleum removal of mercaptans with airborne oxygen oxidation mercaptan, reaches described purpose.For heterogeneous catalyst, according to this method, can use water-soluble mantoquita, molysite, nickel salt or cobalt salt, its quantity is about 0.01 to about 10.0% (quality), be deposited on the fibrous carbon material of fabric type material, felt or rope, described fibrous carbon material contains the oxide of different price metal, and this method is carried out under about 220 ℃ about 80.
For this reason, use the carbon fibre material of the oxide of calcic, magnesium, copper, manganese, iron, zinc and aluminium, the consumption of oxide will provide enough alkalescence for mercaptan oxidation takes place.Usually, about at the most 0.03% (quality) of its consumption.
The distinguishing feature of the method that is proposed is to use to contain to have an appointment and 0.01 is deposited on heterogeneous catalyst on the material that carbon fibre forms to the water-soluble mantoquita of about 10.0% (quality), molysite, nickel salt or cobalt salt; Use the carbon fibre material of textile fabric (cloth), felt or rope (twisted filament) form, contain 0.03% (quality) different price metal oxide at the most, and this process is carried out under about 220 ℃ about 80.
The described distinguishing feature of the method that is proposed has been determined its novelty, significantly be different from the method for this professional known systems level, because water-soluble mantoquita, molysite, nickel salt or cobalt salt were not described as the carrier of catalyst in the literature as catalyst and the carbon fibre material that contains textile fabric, felt or rope (twisted filament) form of different price metal oxide, and they make the method for fraction oil of petroleum removal of mercaptans that higher mercaptan oxidation degree be arranged, and prolong and need not use alkali the service life of catalyst.
The example of water-soluble mantoquita, molysite, nickel salt or cobalt salt includes but not limited to the inorganic acid salt of these metals, as sulfate, chloride and nitrate.Also can use phenylate (be Ph-O-Me-O-Ph, wherein Me is a metal, and Ph is a phenyl).For example, copper sulphate, copper chloride, phenylate copper, ferric sulfate, nickel nitrate and cobalt nitrate are useful in enforcement of the present invention, and phenylate copper is particularly preferred, because it can not brought in the product behind the removal of mercaptans.
Water-soluble mantoquita, molysite, nickel salt or the cobalt salt quantity on the carbon fibre material that proposes is 0.01 to be necessary with enough to about 10.0% (quality).Because, can not reach required mercaptan oxidation degree when the content of water-soluble mantoquita, molysite, nickel salt or cobalt salt during less than 0.01% (quality).Simultaneously, the upper limit of water-soluble mantoquita, molysite, nickel salt or cobalt salt content (10.0% (quality)) is by the absorption property decision of carbon fibre material to water-soluble mantoquita, molysite, nickel salt or cobalt salt.
The use that contains the carbon fibre material of about at the most 0.03% (weight) different price metal oxide makes used catalyst produce the necessary alkalescence with enough becomes possibility, does not therefore need to use in the method alkaloid substance.
Be applicable to that typical different price metal oxide of the present invention includes but not limited to the oxide of calcium, magnesium, iron, manganese, copper, zinc and aluminium.Usually, these oxides are water-fast or only water-soluble slightly.
The carbon fibre material that contains textile fabric, felt or rope (twisted filament) form of about at the most 0.03% (weight) different price metal oxide is immersed in this material in the solution of above-mentioned slaine in industrial usefulness, and the method for heat-treating is subsequently produced.
By under about 220 ℃, carrying out this method about 80, removal of mercaptans for fraction oil of petroleum, might be under situation about not cooling off in advance, in fraction oil of petroleum, carry out mercaptan oxidation under the temperature in action, thus improved mercaptan oxidation degree, reduced energy consumption and reduced relevant energy cost.
The catalyst that is proposed is according to the preparation of known method, and the carbon fibre material that is about to contain the oxide of calcium, magnesium, copper, manganese, iron, zinc and aluminium is immersed in mantoquita, molysite, nickel salt or the cobalt saline solution of desired concn, carries out drying subsequently.
The method that is proposed is applicable among the various embodiment that comprise model mixture, gasoline fraction (60～180 ℃ of boiling ranges), kerosene distillate (120～240 ℃) and the diesel oil distillate (180～350 ℃) of n-dodecyl mercaptan in dodecane under laboratory condition.
With following embodiment method of the present invention is described.
Embodiment 1
The heterogeneous catalyst that 5g is contained 10% (quality) copper sulphate/carbonaceous fabric is packed in the batch reactor, and carbon fibre also contains the oxide of 0.03% (quality) calcium, magnesium, copper, manganese, iron, zinc and aluminium.By be dipped to saturated method with the aqueous solution copper sulphate is deposited on the carbon fibre.Then the model mixture of 35ml n-dodecyl mercaptan in dodecane packed in the reactor.
Reactor is the hydrostatic column that glass is made, and capacity is 100ml, uses the metal spiral heating tube from external heat.Air is sent into reactor from the bottom; This air disperses at space reactor equably by the Schott filter, and filter is contained in the bottom of reactor.With airborne oxygen oxidation mercaptan, air feed speed is 0.5 liter/minute under 100 ℃, normal pressure.Oxidization time is 4 minutes.
Content with mercaptan sulfur in potentiometric determination raw material and the refined products.
Experimental result is listed table 1 in.
Embodiment 2～13
Carry out the removal of mercaptans of the model mixture of lauryl mercaptan in dodecane with being similar to embodiment 1 described method.The composition and the experimental result of catalyst are listed table 1 in.
Carry out the removal of mercaptans of the model mixture of lauryl mercaptan in dodecane with being similar to embodiment 1 described method.The composition and the experimental result of catalyst are listed table 1 in.
Embodiment 14-16
With being similar to embodiment 1 described method in the presence of known catalysts, carry out the removal of mercaptans of the model mixture of lauryl mercaptan in dodecane.Experimental result is listed table 1 in.
Embodiment 17
Under as embodiment 1 described the same terms, in the presence of the described heterogeneous catalyst that contains 1% (quality) copper sulphate/carbonaceous fabric of embodiment 1, the carbonaceous fabric contains 0.03% (quality) metal oxide, under 220 ℃, mercaptan sulfur content is that the diesel oil distillate of 0.02% (quality) carries out 5 minutes removal of mercaptans.The analysis showed that through the diesel oil distillate of removal of mercaptans the residual content of mercaptan sulfur is 0.0005% (quality).Simultaneously, the degree of oxidation of mercaptan is 97.5% in the diesel oil distillate.
Embodiment 18
Under as embodiment 1 described the same terms, in the presence of the known heterogeneous catalyst and 20% aqueous slkali that contain 0.5% (quality) disulfo peptide cyanines cobalt/carbonaceous fabric (no metal oxide), under 220 ℃, mercaptan sulfur content is that the diesel oil distillate of 0.02% (quality) carries out 5 minutes removal of mercaptans.The analysis showed that through the diesel oil distillate of removal of mercaptans the residual content of mercaptan sulfur is 0.0075% (quality).Simultaneously, the degree of oxidation of mercaptan is 62.5% in the diesel oil distillate.
Embodiment 19
Under as embodiment 1 described the same terms, containing in the presence of the described heterogeneous catalyst that contains 1% (quality) copper sulphate/carbonaceous fabric of embodiment 1, the carbonaceous fabric contains 0.03% (quality) metal oxide, and mercaptan sulfur content is that the gasoline fraction of 0.077% (quality) continues 3 minutes removal of mercaptans.The analysis showed that through the gasoline fraction of removal of mercaptans the residual content of mercaptan sulfur is 0.0001% (quality).Simultaneously, the degree of oxidation of mercaptan is 99.87% in the gasoline fraction.
Embodiment 20
Under as embodiment 1 described the same terms, in the presence of the known heterogeneous catalyst and 20% aqueous slkali that contain 0.5% (quality) disulfo phthalocyanine cobalt/carbonaceous fabric (no metal oxide), under 80 ℃, mercaptan sulfur content is that the gasoline fraction of 0.077% (quality) continues removal of mercaptans 3 minutes.
The analysis showed that through the gasoline fraction of removal of mercaptans residual sulphur content is 0.028% (quality).
Simultaneously, the degree of oxidation of mercaptan is 63.6% in the gasoline fraction.
Table 1
** to going out example
| Embodiment | Catalyst is formed | Oxidization time divides | Mercaptan sulfur content in the raw material, % (quality) | Refining degree | |
| Before refining | After refining | ||||
| 1 | 10% (quality) copper sulphate/contain carbon fiber of 0.03% (quality) metal oxide | 4 | 0.015 | Do not have | 100 |
| 2 | 1% (quality) copper sulphate/contain carbon fiber of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0001 | 99.8 |
| 3 | 0.1% (quality) copper sulphate/contain carbon fiber of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0012 | 92.2 |
| 4 | 0.01% (quality) copper sulphate/contain carbon fiber of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0032 | 78.2 |
| 5 | 1% (quality) copper sulphate/contain carbon fiber of 0.01% (quality) metal oxide | 4 | 0.015 | 0.001 | 93.3 |
| 6 | 1% (quality) copper sulphate/contain carbon fiber of 0.02% (quality) metal oxide | 4 | 0.015 | 0.0002 | 98.7 |
| 7 | 10% (quality) copper sulphate/contain carbonaceous felt of 0.03% (quality) metal oxide | 4 | 0.015 | Do not have | 100 |
| 8 | 1% (quality) copper sulphate/contain carbonaceous felt of 0.03% (quality) metal oxide | 4 | 0.015 | Do not have | 100 |
| 9 | 0.1% (quality) copper sulphate/contain carbonaceous felt of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0006 | 96.0 |
| 10 | 1% (quality) copper sulphate/contain carbon fabric of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0021 | 86.0 |
| 11 | 1% (quality) nickel nitrate/contain carbon fabric of 0.03% (quality) metal oxide | 4 | 0.015 | Do not have | 100 |
| Embodiment | Catalyst is formed | Oxidization time divides | Mercaptan sulfur content in the raw material, % (quality) | Refining degree | |
| Before refining | After refining | ||||
| 12 | 1% (quality) cobalt nitrate/contain carbonaceous fabric of 0.03% (quality) metal oxide | 4 | 0.015 | 0.0007 | 95.5 |
| 13 | 1% (quality) copper chloride/contain carbonaceous fabric of 0.03 metal oxide | 4 | 0.015 | Do not have | 100 |
| 14* | The carbonaceous fabric and 5ml 2.5% sodium hydrate aqueous solution of 1% (quality) disulfo phthalocyanine cobalt/no metal oxide | 4 | 0.015 | 0.0031 | 79.5 |
| 15* | Carbonaceous fabric of 0.5% (quality) four sulfo group phthalocyanine cobalt/no metal oxides and 5ml 2.5% sodium hydrate aqueous solution | 4 | 0.015 | 0.00285 | 81.0 |
| 16* | The carbonaceous fabric and 5ml 2.5% sodium hydrate aqueous solution of 0.5% (quality) four sulphur device phthalocyanine cobalt/no metal oxides | 4 | 0.015 | 0.0029 | 80.5 |
In the listed experimental data of table 1 with on the basis of embodiment 17～20, as can be seen, compare with known method, by carrying out processing method of the present invention, the degree of oxidation (improving 15～35%) of mercaptan in the fraction oil of petroleum might be significantly improved, and this method might be under the situation of not using alkaloid substance, carried out.
Following examples explanation catalyst still keeps high catalytic activity after long-term the use.
Embodiment 21
Under as embodiment 1 described the same terms, contain at 3g in the presence of the heterogeneous catalyst of 1% (quality) copper sulphate/carbonaceous fabric, the carbonaceous fabric contains 0.03% (quality) metal oxide, and the kerosene distillate that contains mercaptan sulfur content 0.0082% quality (120～240 ℃) that is obtained by the Ryazan oil plant carries out 10 minutes removal of mercaptans.Take out refining kerosene, pour fresh kerosene into reactor, carry out oxidation.This process repeats tens of circulations.In similar method, in the presence of known catalysts, carry out the kerosene distillate removal of mercaptans.Experimental result is listed table 2 in.
On the basis of the listed experimental data of table 2, as can be seen, compare with known method, under the condition of using repeatedly, the method that is proposed can reach high activity of such catalysts stability, need not regenerate.
Compare with known method, the described advantage of the method that is proposed is significantly increased the technical-economic index of described method.
Table 2
* Comparative Examples
| Embodiment | Catalyst is formed | Oxidization time divides | Mercaptan sulfur content in the raw material, % (quality) | Refining degree | |
| Before refining | After refining | ||||
| 21 | 1% (quality) copper sulphate/contain carbonaceous fabric of 0.03% (quality) metal oxide | 1 2 3 4 5 | 0.0082 | Do not have | 100 |
| 22* | 1% (quality) disulfo CuPc/not the carbonaceous fabric and 5ml 2.5% sodium hydrate aqueous solution of containing metal oxide | 1 2 3 4…50 | 0.0082 | 0.00205 0.0022 0.00243 0.00281…0.0036 | 75.0 72.9 70.4 65.7…55.9 |
Claims (9)
- One kind in the presence of heterogeneous catalyst, by make the method for the fraction oil of petroleum removal of mercaptans that contains mercaptan with the described mercaptan of airborne oxygen oxidation, described method is included in the heterogeneous catalyst that contains the water-soluble mantoquita of 0.01 to 10.0% (quality), molysite, nickel salt or cobalt salt and exists down, described mercaptan contacts with oxygen, described water soluble salt is deposited on the fibrous carbonaceous material, and described material contains the different price metal oxide of the oxide that is selected from calcium, magnesium, iron, manganese, copper, zinc and aluminium of 0.03% (quality) at the most.
- 2. according to the process of claim 1 wherein that water soluble salt is copper sulphate, copper chloride, phenylate copper, ferric sulfate, nickel nitrate or cobalt nitrate.
- 3. according to the method for claim 2, wherein water soluble salt is a phenylate copper.
- 4. according to the process of claim 1 wherein that the fibrous carbon material is the form of textile fabric, felt or twisted filament.
- 5. according to the process of claim 1 wherein that described method carries out in 80 to 200 ℃ temperature range.
- 6. catalyst, it contains the fibrous carbon material of the different metal oxides of the oxide that is selected from manganese, magnesium, iron, manganese, copper, zinc and aluminium of 0.03% (weight) at the most, and the water-soluble mantoquita of 0.01 to 10.0% (weight), molysite, nickel salt or cobalt salt are deposited on the described material.
- 7. according to the catalyst of claim 6, wherein water soluble salt is copper sulphate, copper chloride, phenylate copper, ferric sulfate, nickel nitrate or cobalt nitrate.
- 8. according to the catalyst of claim 7, wherein water soluble salt is a phenylene ether ketone.
- 9. according to the catalyst of claim 6, wherein the fibrous carbon material is textile fabric, felt or twisted filament form.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/313,635 US5741415A (en) | 1994-09-27 | 1994-09-27 | Method for the demercaptanization of petroleum distillates |
| US08/313,635 | 1994-09-27 | ||
| RU940392/38 | 1994-10-18 | ||
| RU94039238A RU2076892C1 (en) | 1994-10-18 | 1994-10-18 | Method of demercaptanization of oil distillates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155853A CN1155853A (en) | 1997-07-30 |
| CN1071136C true CN1071136C (en) | 2001-09-19 |
Family
ID=26653803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95194720A Expired - Fee Related CN1071136C (en) | 1994-09-27 | 1995-09-26 | A method for the demercaptanization of petroleum distillates |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0783369A4 (en) |
| CN (1) | CN1071136C (en) |
| AU (1) | AU3686195A (en) |
| CA (1) | CA2199373A1 (en) |
| MX (1) | MX9702145A (en) |
| NO (1) | NO971379D0 (en) |
| WO (1) | WO1996009891A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320958C (en) * | 2005-05-30 | 2007-06-13 | 北京三聚环保新材料有限公司 | Double-effect catalyst and its production process |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067709C (en) * | 1998-10-23 | 2001-06-27 | 中国石化广州石油化工总厂 | Process of demercaptaning for gasoline by catalyst cracking |
| CN1961061A (en) * | 2004-05-31 | 2007-05-09 | 新加坡科技研究局 | Novel process for removing sulfur from fuels |
| US8016999B2 (en) | 2004-05-31 | 2011-09-13 | Agency For Science, Technology And Research | Process for removing sulfur from fuels |
| US9068128B2 (en) * | 2011-10-18 | 2015-06-30 | Baker Hughes Incorporated | Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028269A (en) * | 1975-08-21 | 1977-06-07 | Uop Inc. | Process for the preparation of a solid bed catalyst system |
| US4364843A (en) * | 1979-11-28 | 1982-12-21 | Uop Inc. | Catalytic composite, method of manufacture, and process for use |
| US4672047A (en) * | 1984-03-08 | 1987-06-09 | Travis Chandler | Mercaptan oxidation catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL259485A (en) * | 1959-12-28 | |||
| FR2601263B1 (en) * | 1986-07-11 | 1988-11-25 | Total France | NEW CATALYTIC COMPOSITE PRODUCT FOR THE OXIDATION OF MERCAPTANS AND ITS USE FOR THE SOFTENING OF OIL CUTTINGS. |
| JPS63283750A (en) * | 1987-05-14 | 1988-11-21 | Asahi Chem Ind Co Ltd | Catalyst using carbon fibers as carrier |
| JPH05184940A (en) * | 1992-01-14 | 1993-07-27 | Nippon Steel Corp | Catalyst for removing nitrogen oxide, and method and apparatus therefor |
-
1995
- 1995-09-26 CN CN95194720A patent/CN1071136C/en not_active Expired - Fee Related
- 1995-09-26 AU AU36861/95A patent/AU3686195A/en not_active Abandoned
- 1995-09-26 MX MX9702145A patent/MX9702145A/en not_active IP Right Cessation
- 1995-09-26 EP EP95934553A patent/EP0783369A4/en not_active Withdrawn
- 1995-09-26 CA CA002199373A patent/CA2199373A1/en not_active Abandoned
- 1995-09-26 WO PCT/US1995/012339 patent/WO1996009891A1/en not_active Application Discontinuation
-
1997
- 1997-03-24 NO NO971379A patent/NO971379D0/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028269A (en) * | 1975-08-21 | 1977-06-07 | Uop Inc. | Process for the preparation of a solid bed catalyst system |
| US4364843A (en) * | 1979-11-28 | 1982-12-21 | Uop Inc. | Catalytic composite, method of manufacture, and process for use |
| US4672047A (en) * | 1984-03-08 | 1987-06-09 | Travis Chandler | Mercaptan oxidation catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320958C (en) * | 2005-05-30 | 2007-06-13 | 北京三聚环保新材料有限公司 | Double-effect catalyst and its production process |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9702145A (en) | 1997-06-28 |
| CA2199373A1 (en) | 1996-04-04 |
| NO971379L (en) | 1997-03-24 |
| CN1155853A (en) | 1997-07-30 |
| WO1996009891A1 (en) | 1996-04-04 |
| NO971379D0 (en) | 1997-03-24 |
| AU3686195A (en) | 1996-04-19 |
| EP0783369A4 (en) | 1998-12-09 |
| EP0783369A1 (en) | 1997-07-16 |
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